Diguanamines and preparation process, derivatives and use thereof

ABSTRACT

Provided by the present invention are novel diguanamine derivatives, led by 2,5/2,6-bis(4,6-diamino-1,3,5-triazin-2-yl)-bicyclo[2.2.1]heptanes and 1,3/1,4-bis(4,6-diamino-1,3,5-triazin-2-yl)-cyclohexanes, and derivatives thereof, applications of these compounds in fields such as adhesives and paints, utilization of these compounds in flame-retarding, thermal stabilization and compatibilization methods of resins, thermosetting molding compositions and thermosetting expansion-molding compositions making use of these compounds, as well as polymeric microspheres also using these compounds. These compounds are expected to find wide spread industrial utility as various excellent properties can be obtained by using them.

This application is a divisional of application Ser. No. 08/201,391filed on Feb. 24, 1994, which is a continuation-in-part of applicationSer. No. 08/186,550 filed on Jan. 26, 1994, now abandoned, which is acontinuation of application Ser. No. 07/983,855 filed Mar. 2, 1993, nowabandoned.

BACKGROUND OF THE INVENTION Field of the Invention

This invention consists of three invention groups. The first inventiongroup relates to novel diguanamines and diguanamine derivatives as wellas their use in paints, adhesives and the like; the second inventiongroup is concerned with flame-retarding, thermal stabilization andcompatibilization methods of resins, said methods making use of thediguanamines or novel diguanamine derivatives, and also with similarapplications of polymeric microspheres obtained from such diguanamines;and the third invention group pertains to their use as thermosettingmolding compositions and thermosetting expansion-molding compositionsand also to preparation processes of such diguanamines and diguanaminederivatives.

To facilitate understanding of the present invention which involvesthese invention groups, this specification is edited in a somewhatunusual order so that the invention is described group by group exceptfor some descriptions.

FIRST INVENTION GROUP Technical Field

This invention relates to novel diguanamines, which are useful aspolymerizable monomers, as resin raw materials for paint resins,adhesive resins, paper coating resins, fiber treatment resins, powdercoating resins and building materials, as raw materials for guanaminecompound derivatives, as curing agents for epoxy resins and urethaneresins, and as modifiers for high molecular substances such as rubbermaterials. The present invention is also concerned with a preparationprocess of the diguanamines, their derivatives useful as curing agentsand intermediates for various resins, and also with use of thediguanamines and the derivatives thereof.

Background Art

As resin raw materials for paint resins, adhesive resins, paper coatingresins, fiber treatment resins and hide treatments, curing agents forvarious resins, modifiers for rubber materials, modifiers for organicmaterials, and the like, guanamines containing an aminotriazine group,such as melamine and benzoguanamine, have heretofore been used widelyfor their excellent properties including the high hardness and gloss,colorless clearness, great chemical resistance and waterproofness andexcellent abrasion resistance and electrical properties and, as curingagents, for the superb pot life of the resulting resins.

Further, a variety of research and development work has been conductedon such melamines and guanamines containing an aminotriazine group,resulting in the provision of even polyfunctional guanamines whichcontain a tetrafunctional group or a still higher functional group andshow excellent characteristic properties from the viewpoint of theflexibility, toughness, high hardness, waterproofness, curability andthe like of resins.

Such polyfunctional guanamines are absolutely different in structurefrom the novel diguanamines according to the present invention, so thatit is extremely difficult to make a comparison therebetween. For thesake of reference, however, examples which may be given boldly includephthaloguanamine represented by: ##STR1## and spiroguanamine representedby: ##STR2##

The former compound is, however, accompanied by drawbacks such thatresins obtained using it as a raw material are very poor in ultravioletlight resistance and weatherability and cannot hence be used at all asresin raw materials for exterior paints, weatherproof paints, automotivepaints and building resins or are subjected to a considerable limitationupon such applications and that a substantial limitation is also imposedon its use as a raw material for water-base paint resins because thewater reducibility of amino resins formed of phthaloguanamines as itsderivatives is still insufficient in practice although it has beenimproved somewhat over conventional melamine-base amino resins. Thelatter compound, on the hand, is also accompanied by drawbacks such thatresins obtained using it as a raw material have poor inferior heatresistance and poor wheatherability, ultraviolet light resistance andwaterproofness and are difficult to retain their expected functionsoutdoors over a long time as resins for exterior paints, weatherproofpaints, automotive paints and building materials. Further, because ofthe low activity of the amino groups in the latter compound as typified,for example, by the low reaction velocity of the reaction of the lattercompound for the formation of a methylol derivative, the latter compoundalso involves such a problem that a substantial limitation is imposed onthe production of various useful guanamine derivatives, resins and resincuring agents available by reactions of the amino groups and also on theproduction of formaldehyde co-condensation polymers between the lattercompound and compounds such as melamine and benzoguanamine. Moreover, areaction mixture obtained by the formation of a methylol derivative ofthe latter compound can hardly be obtained as a clear solution, leadingto a further drawback such that when employed as a raw material forwater-base resins, for example, water-base paint resins, adhesiveresins, paper coating resins and fiber treatment resins, sufficientproperties can hardly be obtained in the smoothness, curability andphysical properties of the resulting coating films and the reactionmixture cannot be used for such applications or is subjected to aconsiderable limitation in such applications. The latter compound isaccompanied by a still further drawback such that production ofspironitrile as a starting material for the preparation of the lattercompound involves not only technical problems such as the need for manycomplex steps including a cumbersome purification step but also asubstantial impairment in economy. As has been described above, thesecompounds have been subjected to significant technical and economicallimitations upon their use and preparation.

DISCLOSURE OF THE INVENTION

With the foregoing drawbacks in view, the present inventors haveproceeded with an extensive investigation. As a result, diguanaminestotally different in structure and characteristic properties from themulti-functional diguanamines described above for the sake of referencehave been found. These diguanamines contain active amino groups whichshow excellent reactivity to compounds having various functional groups.Owing to the inclusion of eight active hydrogen atoms, the degree ofmethylol derivation and the like can be selected from a wide range. Theyare excellent in weatherability, ultraviolet light resistance and thelike, so that they can retain their expected functions outdoors or undersimilar conditions over a long time. Further, their methylol derivativesare excellent in properties such as water dilution, curability,waterproofness, antifouling property, flexibility, hardness andtoughness. An excellent process for the preparation of such diguanamineshas also been found. According to the process, each target diguanaminecompound can be obtained at a high purity with production of byproductsin extremely small amounts and in a high yield from a correspondingdicarbonitrile available at low cost and requires simple preparationsteps such as a simple purification and isolation step. These findingshave led to the present invention.

As derivatives available from such useful diguanamines, the presentinventors have also prepared N-methylol derivatives by reacting thediguanamines with aldehydes, etherified diguanamines by etherificationof the N-methylol derivatives with alcohols, and their initialcondensates. The present inventors have also found curing agents forvarious resins, thermosetting compositions containing these derivativesuseful as raw materials for resins such as paint resins, andthermosetting resin compositions containing the diguanamines andepoxy-containing resins and useful as paint resins, powder coatingresins and adhesive resins, leading to the present invention.

The diguanamines described above are extremely useful compounds, and canprovide polymers, compounds and compositions excellent as rubbermodifiers, optical materials, resist materials, electrical insulatingmaterials, automotive paints, paints for home electric and electronicappliances, antifouling paints, weatherproof paints, fluorescent paints,resinous building materials, powder coatings, water-base paints,oil-base paints, paper coating resins, fiber treatment resins, adhesiveresins, IC packaging resins, anticorrosion resins, polymer modifiers,hide treatments, plastic magnets, latex antioxidants,electrophotographic photoconductors, surfactants, agriculturalchemicals, medicines, etc.

The present invention therefore provides:

(a) a diguanamine represented by the following formula (1): ##STR3##wherein the bonding sites of the 4,6-diamino-1,3,5-triazin-2-yl groupsare the 2,5- or 2,6-positions, or by the following formula (2) whereinthe bonding sites of the 4,6-diamino-1,3,5-triazin-2-yl groups are the1,2-, 1,3- or 1,4-positions;

(b) a process for the preparation of a diguanamine, which comprisesreacting a dicarbonitrile, which is represented by the following formula(3): ##STR4## wherein the bonding sites of the cyano groups are the 2,5-or 2,6-positions, or by the following formula (4): ##STR5## wherein thebonding sites of the cyano groups are the 1,2-, 1,3- or 1,4-positions,with dicyandiamide in the presence of a basic catalyst;

(c) a process for the preparation of a diguanamine, as described aboveunder (b), wherein the basic catalyst is at least one compound selectedfrom the group consisting of alkali metals, alkali metal hydroxides,alkaline earth metal hydroxides, alkali metal alcoholates, alkali metalsalts of dicyandiamide, alkaline earth metal salts of dicyandiamide,amines and ammonia;

(d) a process for the preparation of a diguanamine, as described aboveunder (b), wherein the reaction is conducted using as a reaction solventat least one solvent selected from the group consisting of non-aqueousprotonic solvents and aprotonic polar solvents;

(e) a process for the preparation of a diguanamine, as described aboveunder (b), wherein the reaction is conducted in a temperature range offrom 60° C. to 200° C.;

(f) an N-methylol diguanamine obtained by subjecting the diguanaminedescribed above under (a) and an aldehyde to an addition reaction;

(g) an etherified diguanamine obtained by subjecting the N-methyloldiguanamine derivative as described above under (f) and at least onealcohol selected from alcohols having 1-20 carbon atoms toesterification, said etherified diguanamine containing at least one R₁OCH₂ group wherein R₁ represents a residual group formed by removing ahydroxyl group form the alcohol;

(h) a primary condensate of N-methylol diguanamine obtained bysubjecting the diguanamine described above under (a), a condensablecompound as an optional reactant, and an aldehyde to additioncondensation, having an average addition condensation degree greaterthan 1 and containing at least one methylol group;

(i) a primary condensate of etherified diguanamine obtained bysubjecting the diguanamine described above under (a), a condensablecompound as an optional reactant and an aldehyde to an addition reactionor addition condensation reaction and then subjecting the reactionproduct and at least one alcohol selected from alcohols having 1-20carbon atoms to etherification and optionally to simultaneouscondensation, having an average addition condensation degree greaterthan 1 and containing at least one R₁ OCH₂ group wherein R₁ has the samemeaning as defined above);

(j) a thermosetting composition comprising, as an essential component,at least one compound selected from the group consisting of theN-methylol diguanamines as described above under (f), the etherifieddiguanamines as described above under (g), the primary condensates ofthe N-methylol diguanamines described above under (h), and the primarycondensates of the etherified diguanamines described above under (i);

(k) a thermosetting composition as described above under (j), furthercomprising a resin curable through a reaction with the componentdescribed above under (j);

(l) a paint resin composition comprising the thermosetting compositiondescribed above under (k);

(m) a thermosetting resin composition comprising the diguanamine asdescribed above under (a) and an epoxy-containing resin;

(n) a paint resin composition comprising the thermosetting resincomposition described above under (m);

(o) a paint resin composition as described above under (n), saidcomposition being a powder coating resin composition; and

(p) an adhesive resin composition comprising the thermosetting resincomposition as described above under (m).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an infrared absorption spectrum of a compound obtained inExample 1;

FIGS. 2A and 2B are a mass spectrum of the compound obtained in Example1;

FIG. 3 is an infrared absorption spectrum of a compound obtained inExample 3; and

FIGS. 4A and B are a mass spectrum of the compound obtained in Example3.

BEST MODE FOR CARRYING OUT THE INVENTION

In the diguanamine (1) according to this invention, the bonding sites ofthe 4,6-diamino-1,3,5-triazin-2-yl groups are the 2,5- or 2,6-positions.The configuration of such groups is an endo--endo form, end-exo form orexo--exo form. These stereoisomers are all useful compounds.

Although the diguanamine (1) is a compound selected from the groupconsisting of the above-described isomers in bonding sites orconfiguration, mixtures of different compounds selected from such agroup are also extremely useful from the industrial viewpoint like theindividual compounds.

Specific examples of the diguanamine (1) include, but are not limitedto, 2,5-bis(4,6-diamino-1,3,5-triazin-2-yl)-bicyclo[2.2.1]heptane(end-exo form),2,5-bis(4,6-diamino-1,3,5-triazin-2-yl)-bicyclo[2.2.1]-heptane (exo--exoform), 2,6-bis(4,6-diamino-1,3,5-triazin- 2-yl)-bicyclo[2.2.1]heptane(endo--endo form), and2,6-bis(4,6-diamino-1,3,5-triazin-2-yl)-bicyclo-[2.2.1]heptane (exo--exoform).

In the diguanamine (2) according to this invention, the bonding sites of4,6-diamino-1,3,5-triazin-2-yl groups are the 1,2-, 1,3- or1,4-positions. The configuration of such groups are either a trans formor a cis form. These stereoisomers are all useful compounds.

Although the diguanamine (2) is a compound selected from the groupconsisting of the above-described isomers in bonding sites orconfiguration, mixtures of different compounds selected from such agroup are also extremely useful from the industrial viewpoint like theindividual compounds.

Specific examples of the diguanamine (2) include, but are not limitedto, 1,2-bis(4,6-diamino-1,3,5-triazin-2-yl)-cyclohexane (cis form),1,2-bis(4,6-diamino-1,3,5-triazin-2-yl)-cyclohexane (trans form),1,3-bis(4,6-diamino-1,3,5-triazin-2-yl)-cyclohexane (trans form),1,3-bis(4,6-diamino-1,3,5-triazin-2-yl)-cyclohexane (cis form),1,4-bis(4,6-diamino-1,3,5-triazin-2-yl)-cyclohexane (trans form), and1,4-bis-(4,6-diamino-1,3,5-triazin-2-yl)-cyclohexane (cis form).

Each diguanamine according to the present invention can be obtained, forexample, by a process in which a dicarbonitrile represented by thefollowing formula (3): ##STR6## wherein the bonding sites of the cyanogroups are the 2,5- or 2,6-positions, or

by the following formula (4): ##STR7## wherein the bonding sites of thecyano groups are the 1,2-, 1,3- or 1,4-positions is reacted withdicyandiamide in the presence of a basic catalyst or by a process inwhich an ester of a dicarboxylic acid corresponding to thedicarbonitrile and a biguanide are reacted optionally in the presence ofa basic compound. The former process is excellent both technically andeconomically and is extremely practical, because the raw materials arereadily available and are easy to handle, byproducts are minimized andthe target compound can be obtained with high purity, preparationincluding a purification step is simple, the loss of the raw materialsis very small, and the target compound can be obtained in a high yield.It is however to be noted that the preparation process of thediguanamine is not necessarily limited to these processes.

In the dicarbonitrile (3) in the preparation process of the diguanamine,said process pertaining to this invention, the bonding sites of thecyano groups are the 2,5- or 2,6-positions. The configuration of thesegroups is an endo-endo form, endo-exo form or exo-exo form. Thesestereoisomers are all useful. Although the dicarbonitrile (3) is acompound selected from the group consisting of the above-describedisomers in bonding sites or configuration, mixtures of differentcompounds selected from such a group are also useful like the individualcompounds.

The dicarbonitrile (3) can be obtained, for example, by a process inwhich bicyclo[2.2.1]hepta-5-ene-2-carbonitrile and a hydrogen cyanideare reacted in the presence of a particular catalyst such as Co₂ (CO)₈,Fe(CO)₅ or Ni[P(OC₆ H₅)₃ ]₄ as disclosed in U.S. Pat. No. 2,666,748 orthe like, by a process in which 5-(and/or6-)cyano-bicyclo[2.2.1]hepta-2-carbaldehyde and a hydroxylamine arereacted as disclosed in U.S. Pat. No. 3,143,570 or the like, or by aprocess in which 2,5- (and/or 2,6-)dichloro-bicyclo[2.2.1]heptane and acyanating agent such as an alkali metal cyanate or alkaline earth metalcyanate are reacted. It is however to be noted that the preparationprocess is not limited to such processes.

Specific examples of the dicarbonitrile (3) include, but are not limitedto, bicyclo[2.2.1]heptane-2,5-dicarbonitrile (endo-exo form),bicyclo[2.2.1]-haptane-2,5-dicarbonitrile (endo-endo form),bicyclo[2.2.1]heptane-2,6-dicarbonitrile (endo-exo form), andbicyclo[2.2.1]heptane-2,6-dicarbonitrile (exo--exo form).

In the dicarbonitrile (4) in the preparation process of the diguanamine,said process pertaining to this invention, the bonding sites of thecyano groups are the 1,2-, 1,3- or 1,4-positions. The configuration ofthese groups is either a trans form or a cis form. These stereoisomersare all useful compounds. Although the dicarbonitrile (4) is a compoundselected from the group consisting of the above-described isomers inbonding sites or configuration, mixtures of different compounds selectedfrom such a group are also useful like the individual compounds.

The dicarbonitrile (4) can be obtained, for example, by a process inwhich 4-cyanocylohexene and hydrogen cyanide are reacted in the presenceof a catalyst such as Ni[P(OC₆ H₅)₃ ]₄ as disclosed in U.S. Pat. No.3,496,217 or the like, by a process in which 3- (and/or4-)cyano-cyclohexanecarbaldehyde and a hydroxylamine are reacted asdisclosed, by a process in which a dihalogenated cyclohexanecorresponding to the dicarbonitrile (4) and a cyanating agent such as analkali metal cyanate or alkaline earth metal cyanate are reacted, by aprocess in which a dicarboxylic acid corresponding to the dicarbonitrile(4) or the diammonium salt, diamide or diester derivative of thedicarboxylic acid and ammonia are reacted using a dehydrating agent suchas alumina catalyst or thionyl chloride, or by a process in which1-cyanocyclohexene and hydrogen cyanide are reacted in the presence ofan alkali such as sodium hydroxide. It is however to be noted that thepreparation process is not limited to such processes.

Specific examples of the dicarbonitrile (4) include, but are not limitedto, 1,2-cyclohexanedicarbonitrile (trans form),1,3-cyclohexanedicarbonitrile (trans form),1,3-cyclohexanedicarbonitrile (cis form), 1,4-cyclohexanedicarbonitrile(trans form), and 1,4-cyclohexanedicarbonitrile (cis form).

In the process of the present invention for the preparation of thediguanamine, the molar ratio of the dicarbonitrile to dicyandiamide tobe reacted with each other can be chosen suitably as needed. The molarratio of the dicarbonitrile to dicyandiamide to be reacted with eachother is 1:2 stoichiometrically. Use of dicyandiamide at an unduly smallmolar ratio relative to the dicarbonitrile is not preferred because theyield of the diguanamine according to this invention becomes low and,moreover, the corresponding monoguanamine [1:1 (by molar ratio) reactionproduct of the dicarbonitrile and dicyandiamide] is formed more and thepurification step and the like thus become irksome. Use of dicyandiamideat an unduly large molar ratio makes irksome the removal, separation andthe like of unreacted dicyandiamide, etc. Use of dicyandiamide at suchan unduly small or large molar ratio is therefore not preferred bothtechnically and economically. With a view toward improving the yield ofthe diguanamine according to the present invention and also simplifyingthe process including the purification step, it is generally desired toreact 1.5-10.0 moles, preferably 2.0-5.0 moles of dicyandiamide with 1mole of the dicarbonitrile.

Examples of the basic catalyst in the process of the present inventionfor the preparation of the diguanamine include alkali metals such aspotassium and sodium; alkali metal and alkaline earth metal hydroxidessuch as lithium hydroxide, potassium hydroxide, sodium hydroxide,calcium hydroxide and barium hydroxide; alkali metal and alkaline earthmetal carbonates such as potassium carbonate, sodium carbonate andbarium carbonate; alkali metal alcoholates such as potassium ethylate,sodium methylate and sodium ethylate; alkali metal and alkaline earthmetal salts of dicyandiamide; amines such as1,8-diazabicyclo-[5.4.0]undecene-7, triethylenediamine, piperidine,ethylenediamine, diethylenetriamine, pyrrolidone andtetrahydroquinoline; and ammonia. Particularly preferred are alkalimetals, alkali metal hydroxides, alkaline earth metal hydroxides, alkalimetal alcoholates, the alkali metal salts of dicyandiamide, the alkalineearth metal salts of dicyandiamide, amines and ammonia. They can be usedeither singly or in combination. Although no particular limitation isimposed on the amount of such a catalyst, it can be added in an amountof 500-0.001 mole %, preferably 300-0.1 mole % based on thedicarbonitrile from the viewpoint of preparation conditions and economy.The amount of the catalyst can be chosen suitably as needed.

In the above process for the preparation of the diguanamine, it isextremely practical to conduct the process while using one of varioussolvent as a reaction solvent in order to perform the reaction moresmoothly. It is however not preferred to use any solvent which mayinduce the formation of a compound other than the target compound or maycause an inhibition on the reaction, for example, a solvent such as afatty acid, a fatty acid anhydride, trifluoroacetic acid, liquid sulfurdioxide, sulfuryl chloride, a mineral acid or water.

Illustrative of the reaction solvent include alcohols such as methanol,ethanol, n-propanol, isopropanol, n-butanol, iso-butanol, tert-butanol,2-ethylhexanol, dodecyl alcohol, allyl alcohol, propargyl alcohol,benzyl alcohol, cyclohexanol, ethylene glycol, butanediol, glycerin,1,2,6-hexanetriol, 2-methoxyethanol, 2-ethoxyethanol,2-isopropoxyethanol, 2-butoxyethanol, furfuryl alcohol,tetrahydrofurfuryl alcohol, diethylene glycol, diethylene glycolmonomethyl ether, methylene glycol monobutyl ether,1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, diacetonealcohol, 2,2,2-trifluoroethanol and 1,3-dichloro-2-propanol; ketomassuch as acetone, methyl ethyl ketone, methyl isobutyl ketone andacetophenone; esters such as ethyl acetate, butyl acetate and benzylacetate; ethers such as diethyl ether, ethylene glycol dimethyl ether,diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, crown ethersand anisol; carboxylic acid amides such as N,N-dimethylformamide,N,N-diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and1,3-dimethyl-2-imidazolidinone; sulfolanes such as sulfolane,methylsulfolane and 1,3-propanesultone; sulfoxides such as dimethylsulfoxide; amines such as methylamine, dimethylamine, trimethylamine,ethylamine, diethylamine, triethylamine, isopropylamine, butylamine,2-ethylhexylamine, allylamine, aniline, cyclohexylamine, pyridine,piperidine, monoethanolamine, 2-(dimethylamino)ethanol, diethanoiamine,triethanolamine, isopropanolamine and triisopropanolamine; and ammonia.Particularly preferred are non-aqueous protonic solvents such asalcohols, amines and ammonia and aprotonic polar solvents such ascarboxylic acid amides, sulfolanes and sulfoxides. These solvents can beused either singly or as mixed systems consisting of two or more of themlike mixed solvents such as ammonia-alcohol anddimethylsulfoxidecellosolve. They can be chosen suitably as needed. Suchsolvents preferably have a water content as low as possible, notably awater content of 1.0 wt. % or less.

Reaction temperatures not higher than 60° C. are not preferred, becausethe reaction is extremely slow so that a long time is required for thepreparation and the yield is very low. When the reaction is conductedgenerally at a temperature of 60° C. or higher, preferably at atemperature of 80° C. or higher, the reaction proceeds promptly andsmoothly so that the target compound can be obtained in a high yield.However, if the reaction temperature exceeds about 200° C., theformation of byproducts suddenly increases to such an extent that thesebyproducts can no longer be ignored, and the purity of the product islowered considerably. Reaction temperatures above 200° C. are thereforenot preferred. In the process of this invention for the preparation ofthe diguanamine, it is therefore preferred to conduct the reaction in atemperature range of 60°-200° C., more preferably 80°-180° C. In such atemperature range, byproducts are minimized and the target compound canbe obtained with high purity, the preparation including the purificationcan be performed easily, and the target compound can be obtained in ahigher yield.

Although no particular limitation is imposed on the reaction system, thereaction can be carried out either under normal pressure or undernaturally-occurring pressure or elevated pressure in a closed vessel.The reaction system can be suitably selected as needed.

To obtain the diguanamine of the present invention, that is, the targetcompound from the reaction mixture of the above reaction, it is mostdesirable to cool the reaction mixture and collect the crystallizeddiguanamine by filtration. As an alternative, the reaction mixture maybe poured, as is, into hot water, followed by crystallization andfiltration. Unreacted dicyandiamine and/or dicarbonitrile, whichaccompany with the crude diguanamine, can be easily removed by washingthe crude diguanamine with hot water or methanol. When furtherpurification is required depending on the application purpose, thediguanamine can be purified further by subjecting to recrystallizationin the above-described reaction solvent, for example, an alcohol,cellosolve, carboxylic acid amide, sulfolane or sulfoxide, a mixedsolvent of such a solvent and water, or water; by dissolving it in theabove-described reaction solvent and then pouring the resultant solutionin hot water, thereby effecting reprecipitation; or by dissolving thecrude diguanamine in an HCl-acidified aqueous solution and mixing theresulting solution with an alkali, thereby re-precipitating thediguanamine. Such additional purification is however not requiredpractically in most instances, because the yield is extremely good inthe process of this invention for the preparation of the diguanamineand, moreover, the diguanamine can be obtained with high puritysufficient for practical applications when washed simply with one ofvarious solvents such as methanol, water, a mixed solvent thereof or thelike.

The diguanamine according to the present invention has excellentpolymerizability with various compounds such as aldehydes, epoxycompounds, carboxylic acids and isocyanates and also has variousexcellent reactivity, so that the diguanamine is extremely useful as araw material for resins and also as a raw material for derivatives.Moreover, diguanamine derivatives such as reaction products of thediguanamine with aldehydes, reaction products obtained by etherifyingthe first-mentioned reaction products with alcohols, and reactionproducts obtained by subjecting the first-mentioned and second-mentionedreaction products to condensation are particularly useful as curingagents and raw materials for various resins.

Such diguanamine derivatives include, for example, the above-describedderivatives:

(f) N-methylol diguanamine obtained by subjecting the diguanaminedescribed under (a) and an aldehyde to an addition reaction andrepresented by the following formula (5) or (6): ##STR8## wherein thebonding sites of the N-substituted-4,6-diamino-1,3,5-triazin-2-yl groupsare the 2,5- or 2,6-positions, R₂, R₃, R₄, R₅, R₆, R₇ and R₈individually represent one substituent selected from a hydrogen atom andan HOCH₂ group, and R₂, R₃, R₄, R₅, R₆, R₇ and R₈ may be the same ordifferent, or ##STR9## wherein the bonding sites of theN-substituted-4,6-diamino-1,3,5-triazin-2-yl groups are the 1,2-, 1,3-or 1,4-positions, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ have the same meaning asdefined above, and R₂, R₃, R₄, R₅, R₆, R₇ and R₈ may be the same ordifferent;

(g) etherified diguanamines each obtained by etherifying the N-methyloldiguanamine described above under (f) with at least one alcohol selectedfrom the group consisting of alcohols having 1-20 carbon atoms,containing at least one R₁ OCH₂ group, R₁ representing a residual groupformed by removing a hydroxyl group from the alcohol, and represented bythe following formula (7) or (8): ##STR10## wherein the bonding sites ofthe N-substituted-4,6-diamino-1,3,5-triazin-2-yl groups are the 2,5- or2,6-positions, R₁ represents a residual group formed by removing ahydroxyl group from the alcohol, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅individually represent one substituent selected from a hydrogen atom andHOCH₂ and R₁ OCH₂ groups, and R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅ may bethe same or different, or ##STR11## wherein the bonding sites of theN-substituted-4,6-diamino-1,3,5-triazin-2-yl groups are the 1,2-, 1,3-or 1,4-positions, R₁ represents a residual group formed by removing ahydroxyl group from the alcohol, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅have the same meaning as defined above, and R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄and R₁₅ may be the same or different;

(h) primary condensates of the N-methylol diguanamine each obtained bysubjecting the diguanamine described above under (a), a condensablecompound as an optional reactant and an aldehyde to an additioncondensation reaction, having an average addition condensation degreegreater than 1 and containing at least one methylol group; and

(i) primary condensates of the etherified diguanamine each obtained bysubjecting the diguanamine described above under (a), a condensablecompound as an optional reactant and an aldehyde to an addition reactionor an addition condensation reaction and then etherifying the reactionproduct with at least one alcohol selected from the group consisting ofalcohols having 1-20 carbon atoms and optionally to a simultaneouscondensation reaction, having an average addition condensation degreegreater than 1 and containing at least one R₁ OCH₂ group, R₁ having thesame meaning as defined above.

Examples of the aldehydes used for the preparation of these derivativesinclude, but are not limited to, formaldehyde, paraformaldehyde,hexamethylenetetramine, methylhemiformal, butylhemiformal,formaldehyde-sodium bisulfite addition product, and glyoxal. Preferredare formaldehyde, formalin, paraformaldehyde, hexamethylenetetramine,methylhemiformal and butylhemiformal.

Useful as the alcohols employed for the etherification in thepreparation of these derivatives are alcohols such as saturated orunsaturated aliphatic alcohols having 1-20 carbon atoms, alicyclicalcohols, alcohols containing one or more ether groups, and alcoholscontaining one or more aromatic groups. Examples of such alcoholsinclude, but are not limited to, methyl alcohol, ethyl alcohol, n-propylalcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol,tert-alcohol, n-hexyl alcohol, sec-heptyl alcohol, 2-ethylhexyl alcohol,n-nonyl alcohol, n-hexadecyl alcohol, n-octadecyl alcohol, n-eicosylalcohol, cyclohexyl alcohol, cyclohexenyl alcohol, 4-methylhexylalcohol, 4-hexylcyclohexyl alcohol, ethylene glycol monomethyl ether,ethylene glycol monobutyl ether, propylene glycol monoisopropyl ether,diethylene glycol monomethyl ether, and benzyl alcohol.

In the preparation of these derivatives, co-condensable compounds can beused in some instances as described above. Examples of suchco-condensable compounds include, but are not limited to, melamine,urea, alkylureas, thiourea, alkylthioureas, aniline, and guanamines suchas benzoguanamine and cyclohexylcarboguanamine.

In the case of the N-methylol diguanamine described above, the reactionproceeds promptly and smoothly to provide the derivative with at leastone HOCH₂ group when the reaction is conducted, for example, in asolvent and, if necessary, in the presence of a basic compound, at pH8.0-13.0, preferably pH 8.5-11.5 and a reaction temperature of not lowerthan 30° C., preferably 40°-80° C. To obtain an N-methylol diguanaminewith a high degree of methylol derivation, the derivative can beobtained with high purity and in a high yield when the reaction isconducted using water and the alcohol in smaller amounts. Use of waterand the alcohol in appropriate amounts, however, leads to a reduction inthe stirring effects, unevenness in the reaction temperature, etc.,thereby making it difficult to smoothly proceeding with the reaction. Itis hence not preferred to reduce the amounts of water and the alcohol.To allow the reaction to proceed smoothly, it is effective to conductthe reaction in the presence of a solvent substantially insoluble inwater and free from inhibition to the reaction, for example, an aromatichydrocarbon such as toluene, xylene, ethylbenzene, cumene or benzene, analiphatic hydrocarbon such as hexane, heptane, octane or cyclohexane, ahalogenated hydrocarbon such as dichloromethane or a aliphatic ethersuch as diisopropyl ether; or to add an amine as an aid, for example, analiphatic amine such as hexamethylenetetramine, piperazine orpiperidine, an aliphatic amine such as triethylamine, diethylamine,dibutylamine or hexylamine, an aromatic amine such as pyridine oraniline, or ammonia in an amount of 0.01-10 mole % based on thealdehyde. The reaction can be performed by suitably choosing thesemethods as needed. It is however to be noted that the practice of thereaction is not necessarily limited to the use of such methods.

The etherified diguanamine described above can be obtained, for example,by reacting the above-obtained N-methylol diguanamine for 1-8 hoursunder acidic conditions of pH 2-4 at a temperature of 40°-80° C. in thepresence of the alcohol with which an etherification reaction is to beconducted. It is particularly preferred to conduct the etherification byreducing the amount of water in the reaction system as much as possibleand charging the reactants at a ratio of at least 20 moles of thealcohol to each mole of the N-methylol diguanamine.

The primary condensate of N-methylol diguanamine described above can beobtained, for example, by reacting with the aldehyde at a temperature of40°-100° C. under conditions of pH 8.0 or lower or pH 13.0 or higher.

Further, the primary condensate of etherified diguanamine can beobtained, for example by subjecting the N-methylol diguanamine or theprimary condensate of N-methylol diguanamine to etherification or toboth etherification and condensation under acidic conditions of pH1.0-5.0 at a temperature of 50°-100° C. in the presence of the alcoholwith which an etherification reaction is to be conducted. It is howeverto be noted that the preparation process is not limited to thatdescribed above.

The N-methylol diguanamine, etherified diguanamine, primary condensateof N-methylol diguanamine and primary condensate of etherifieddiguanamine have excellent reactivity with compounds and resins havingvarious kinds of functional groups and are extremely useful as curingagents for various resins and also as intermediates for resin rawmaterials. For example, it is possible to provide a thermosettingcomposition which comprises at least one derivative selected from thegroup consisting of the derivatives (f), (g), (h) and (i). Although suchcompositions are useful as adhesives, crease resistant finishing agentsfor fibers, for example, synthetic fibers such as polyester fibers andacrylic fibers and natural fibers such as cotton and wool, excellentsurface improving agents for antifouling agents, paper coating agentsand hide treatments even if these derivatives alone are contained ascuring components, these diguanamine derivatives can be reacted furtherwith those containing one or more hydroxyl, carboxyl, isocyanate and/orepoxy groups so that resins having excellent properties can be obtained.In combination with various polymers such as acrylic resins, epoxyresins, polyester resins, urethane resins, aminoalkyd resins, phenolresins, fluorinated resins and vinyl resins, the above derivatives canprovide thermosetting compositions extremely useful as chain extenders,crosslinking agents, curing agents, denature agents and/or modifiers.They are accordingly useful for a wide variety of application fields,for example, as adhesive resins, paint resins and building resins.Especially, thermosetting compositions comprising at least onederivative, which is selected from the group consisting of theN-methylol diguanamines, etherified diguanamines, primary condensates ofthe N-methylol diguanamines and primary condensates of the etherifieddiguanamines, and a resin curable through a reaction with the derivativeare useful as resins for paints such as water-base paints and oil-basepaints.

The resin curable through a reaction with such a derivative can be anyresin having functional groups capable of reacting with the derivativeso that the resin is cured. For example, resins containing at least onetype of groups selected from hydroxyl groups, carboxyl groups, epoxygroups, methylolamido groups, alkoxymethylolamido groups and isocyanategroups are useful. Examples of such resins include, but are not limitedto, acrylic resins, epoxy resins, polyester resins, phenol resins,phenol-alkyd resins, urethane resins, fluorinated resins, siliconeresins, and modified resins thereof.

The diguanamines according to the present invention can providethermosetting resin compositions which comprise, as essentialcomponents, at least one diguanamine selected from the diguanaminesdescribed above and an epoxy-containing resin. A conventionalcomposition comprising an epoxy-containing resin and an amine as acuring agent cures at relatively low temperatures but, because the amineused as a curing agent is chemically active, the amine reacts with theepoxy-containing resin when they are stored as a mixture. This hasresulted in the drawback that the composition has a shorter pot life andits handling is difficult. A composition containing dicyandiamide as acuring agent has relatively good storage stability, but articlesobtained by curing the composition are accompanied by the drawbacks thattheir properties such as flexibility and light resistance are not good.Considerable limitations are therefore imposed on the use of suchcompositions. With these drawbacks in view, the present inventors haveproceeded with an extensive investigation. As a result, they have foundthe above-described thermosetting resin compositions which haveexcellent storage stability and can provide cured resin articles havingexcellent properties as cured products such as excellent flexibility andlight resistance. These thermosetting resin compositions are useful fora wide variety of applications, for example, as IC packaging materials,adhesives, powder coatings, oil-base paints, electric insulatingmaterials and the like.

Any epoxy-containing resin can be used widely in this invention insofaras it contains at least one epoxy group. In general, a polyepoxidecontaining at least two epoxy groups per molecule is preferred. Althoughno particular limitations are imposed on the epoxy-containing resins,illustrative exemplary epoxy-containing resins include, but are notlimited to, diglycidyl ether type epoxy resins of bisphenol A; butadieneepoxide; 4,4-di(1,2-epoxyethyl)diphenyl ether;4,4'-di(epoxyethyl)biphenyl, diglycidyl ether of resorsine; diglycidylether of fluoroglycine; triglycidyl ether of p-aminophenol; triglycidylether of m-aminophenol; tetraglycidyl-bis-(aminophenol)methane;1,3,5-tri(1,2-epoxyethyl)benzene; 2,2,4,4-tetraglycidoxybenzophenone;tetraglycidoxytetraphenylethane; polyglycidyl ethers of novolakphenol-formaldehyde resins; triglycidyl ether of trimethylolpropane;triglycidyl ether of glycerin; diglycidyl ether type epoxy resins ofhalogenated bisphenol A; polyglycidyl ethers of halogenated novolakphenol-formaldehyde resins; cycloaliphatic epoxy resins such asvinylcyclohexene dioxide and 3,4-epoxycyclohexylmethyl3,4-epoxyclohexanecarboxylate; heterocyclic epoxy resins such ashydantoin epoxy resin and triglycidyl isocyanurate; polymers ofepoxy-containing vinyl monomers, such as glycidyl acrylate and glycidylmethacrylate, with copolymerizable vinyl monomers such as acrylateesters, methacrylate esters, fumarate esters, maleate esters,acrylamides, methacrylamides, acrylonitrile, methacrylonitrile,styrenes, butadienes and vinyl esters; and modified polymers thereof.

Where a high-molecular, bisphenol A-diglycidyl ether type epoxy resincannot be used for its high viscosity in the present invention, theresin can be modified using as a modifier such as a low-molecularbisphenol A-glycidyl ether type epoxy resin, bisphenol A, bisphenol S,brominated bisphenol A or brominated bisphenol S.

The mixing ratio of the diguanamine according to this invention to theepoxy-containing resin can be suitably selected depending on theapplication. In general, however, the diguanamine is used in an amountof 0.2-3.0 equivalents, preferably 0.4-1.5 equivalents per equivalent ofepoxy groups in the epoxy-containing resin.

For each thermosetting resin composition according to the presentinvention, a curing accelerator such as a novolak type phenol resin, ametal salt of an organic acid or imidazole can be suitably chosen andmixed. Use of such a curing accelerator is preferred especially where anovolak type phenol resin is used, because a thermosetting resincomposition excellent in storage stability and curability can beobtained. Examples of the novolak type phenol resin include, but are notlimited to, those produced by a process known per se in the art from aphenol such as phenol, cresol, xylenol, ethylphenol, butylphenol,p-phenylphenol, nonylphenol, bisphenol A, resorcinol or chlorophenol andan aldehyde such as formaldehyde or paraformaldehyde. Although themixing proportion of the novolak type phenol resin is generally 0.1-10parts by weight per 100 parts by weight of the epoxy-containing resin,it can be suitably chosen as needed.

The thermosetting resin compositions according to the present inventioncan each be obtained by mechanically mixing a raw material batch, whichis composed of the diguanamine, the epoxy-containing resin and, ifnecessary, other optional components in prescribed mixing proportions,within a Z-blade mixer, extruder, dry ball mill or the like to asufficient extent. Further, the mixture so obtained can be subjected tomelt mixing by hot rolls or the like in some instances. The diguanamineaccording to the present invention, however, has a high melting point sothat the mixture may not flow evenly or the resulting cured article maynot be homogeneous. Even when such melt mixing is not preferred, athermosetting resin composition in a fully compatibilized form can stillbe obtained, for example, by heating, melting and mixing the diguanaminein advance together with a low-viscosity diluent, a solbilizing agent, anovolak type phenol resin, etc., adding an epoxy-containing resin to theresultant melt and then mixing them under heat, by dissolving and mixingthe guanamine and the epoxy-containing resin in a solvent, or byremoving the solvent from the mixed solution. These methods can besuitably chosen as needed. It is to be noted that the present inventionis not necessarily limited to any of these methods.

Besides the diguanamine and epoxy-containing resin described above, eachthermosetting resin composition according to the present invention canbe added, as needed, with an inorganic filler, for example, silicapowder, alumina, antimony trioxide, talc, calcium carbonate, titaniumwhite, clay, mica, red oxide, glass fibers or carbon fibers; a moldrelease agent such as a natural wax, a synthetic wax, a metal salt of afatty acid, an acid amide, an ester or a paraffin; a flame retardantsuch as chlorinated paraffin, bromotoluene, hexabromobenzene or antimonytrioxide; a colorant such as carbon black or red oxide; a silanecoupling agent; a flexibilizer; a viscosity-reducing diluent; one ormore of various curing accelerators; etc.

Each diguanamine according to the present invention can providecompounds and resins such as polyamic acids, polyimides and polyamides,all having excellent properties, when reacted with carboxylic acids, forexample, phthalic acid, adipic acid, maleic acid, trimellitic acid,ethylenetetracarboxylic acid, cyclopentanetetracarboxylic acid,pyrromellitic acid, 3,3',4,4'-benzophenonetetracarboxylic acid,2,2',3,3'-benzophenonetetracarboxylic acid,3,3',4,4'-biphenyltetracarboxylic acid,2,2',3,3'-biphenyltetracarboxylic acid,2,2-bis(3,4-dicarboxyphenyl)propane, bis(2,3-dicarboxyphenyl)methane,2,3,6,7-naphthalenetetracarboxylic acid,1,4,5,8-naphthalenetetracarboxylic acid,1,2,5,6-naphthalenetetracarboxylic acid, 1,2,3,4-benzenetetracarboxylicacid, 2,3,6,7-anthracenetetracarboxylic acid and1,2,7,8-phenanthrenetetracarboxylic acid; or with their precursors,i.e., partial cesters, acid anhydrides, halogenoacylates and the like.Further, each diguanamine according to the present invention can providecompounds and resins such as polyurea, all having excellent properties,when reacted with isocyanates, for example, 1,6-hexamethylenediisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, diisocyanatesderived from dimeric acids, bis(2-isocyanatoethyl) fumarate,methylcyclohexane-2,4-diisocyanate, isophorone diisocyanate,4,4'-dicyclohexylmethane diisocyanate, isopropylidenebis(4-cyclohexylisocyanate), xylylene diisocyanate, m-phenylenediisocyanate, tolidine diisocyanate, dianisidine diisocyanate,3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 1,5-naphthalenediisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate andthe like, or with polyisocyanates which have been obtained by reactingsuch isocyanates with polyols, amines, water or the like. In addition,each diguanamine according to the present invention can also provideresins having excellent properties when reacted with compoundscontaining one or more N-substituted unsaturated imido groups, forexample, with monophenylmaleimide, monophenylcitraconimide,monophenylitaconimide, 2-chlorophenylmaleimide,2,6-dichlorophenylmaleimide, 2-methylphenylmaleimide,2,6-dimethylphenylmaleimide, 4-hydroxyphenylmaleimide,N,N'-ethylenebismaleimide, N,N'-hexamethylenebismaleimide,N,N'-dodecanemethylenebismaleimide, N,N'-m-phenylenebismaleimide,N,N'-p-phenylenebismaleimide, N,N'-p-phenylenebiscitraconimide,N,N'-p-phenylenebisitaconimide,N,N'-p-phenylene-endomethylenetetrahydrophthalimide,N,N'-4,4,-diphenylmethanebismaleimide,2,2-bis[4-(4-maleimidophenoxy)phenyl]propane,N,N'-4,4'-dicyclohexylmethanebismaleimide, N,N'-m-xylenebismaleimide,N,N,-diphenylcyclohexanebismaleimide, 4,4'-bismaleimidocinnamanilide,4,4'-methylene-bis(2-isopropyl-6-methyl-phenylmaleimide) and2,2-bis[4-(4-maleimidophenoxy)phenyl]hexafluoropropane. Further, eachdiguanamine according to the present invention can also be used asmetallic chain extenders, crosslinking agents, curing agents,high-molecular modifiers and the like, which have excellent properties,for various polymers such as urethane resins and epoxy resins. It ishowever to be noted that the use of each diguanamine is not limited tothem.

As has been described above, the diguanamines according to the presentinvention have excellent reactivity and polymerizability with variouscompounds. Such polymerizations, reactions and the like can be conductedby any polymerization or reaction process such as solutionpolymerization, emulsion polymerization, suspension polymerization, bulkpolymerization, interfacial polymerization, solution reaction orwater-system reaction. A suitable polymerization or reaction process canbe chosen as needed.

The diguanamines according to the present invention have specificinherent properties such that they are excellent in weatherability,ultraviolet light resistance and the like and can retain initialperformance outdoors over a long time, their methylol derivatives areextremely good in water reducibility and have excellent properties asraw materials for water-base resins without any substantial limitation,they contain active amino groups having extremely good reactivity withaldehydes, epoxy compounds, carboxylic acids, isocyanates and the like,and owing to the inclusion of eight active hydrogen atoms, permit theselection of a methylol derivation degree from a wide range. Moreover,they can provide various guanamine derivatives and resins havingexcellent properties such as flexibility, toughness, high hardness,waterproofness and curability and can show superb performance, so thatthey are extremely useful compounds.

When the specific compounds described above are used and the reactioncatalyst, solvent, reaction temperature, the molar ratio of the rawmaterials and the like are suitably selected, the process of the presentinvention for the preparation of the diguanamine can obtain the targetproduct with high purity while substantially minimizing byproducts. Thepreparation process including the purification step is simple, cansubstantially reduce the loss of the raw materials, can obtain thetarget product in a high yield from the raw materials availableeconomically, and therefore is excellent in technology and economy andhas extremely high practical utility.

Such diguanamines have excellent polymerizability with various compoundssuch as aldehydes, epoxy compounds, carboxylic acids and isocyanates andalso have various superb reactivity. They are hence extremely useful asraw materials for resins and derivatives. They can provide, for example,derivatives extremely useful as curing agents for various resins andalso as intermediates for resin raw materials, such as N-methyloldiguanamines obtained by reacting the diguanamines with aldehydes,etherified diguanamines obtained by subjecting the N-methyloldiguanamine derivatives and alcohols to etherification, and theirinitial condensates; thermosetting compositions comprising thesederivatives; and thermosetting resin compositions comprising the abovediguanamines and epoxy-containing resins, said compositions being usefulas IC packaging material resins, paint resins and adhesive resins.

The diguanamines according to the present invention are excellentcompounds capable of providing guanamine derivatives, resins andcompositions, which are industrially useful in an extremely wide rangeof fields as rubber modifiers, optical materials, resist materials,electrical insulating materials, paints for home electric and electronicappliances, automotive paints, antifouling paints, anticorrosion paints,weatherable paints, fluorescent paints, powder coatings, water-basepaints, oil-base paints, building materials, IC packaging materials,paper coating agents, fiber treatments for antifouling treatment ofinterior items such as curtains, sofas, wall cloths and carpets and alsofor water vapor barrier treatment, sweat absorption treatment, SPtreatment, wrinkle resistance treatment, water- and oil-repellanttreatment of fibers, adhesive resins, hide treatments, plastic magnets,latex antioxidants, anticorrosion agents, electrophotographicphotoconductors, surfactants, agricultural chemicals, medicines, and thelike.

SECOND INVENTION GROUP Technical Field

This invention relates to modification of resin raw materials, resinsand rubbers--such as polymerizable monomers, polyurethane resins,polyester resins, amino resins, paint resins, adhesive resins, papercoating resins, fiber processing resins, foaming resins, molding resinsand laminates, and specifically to diguanamines and their derivativesand polymeric microspheres, which are useful as flame retardants, heatstabilizers, compatibility improvers or the like for resins. Thisinvention is also concerned with applications of such flame retardants,heat stabilizers and compatibility improvers.

Background Art

In general, resins have excellent properties such as high strength,chemical resistance, abrasion resistance, weatherability, durability anddyeability and, as molded, extruded or otherwise formed resin products,are employed in a wide range of industrial fields such as constructionmaterial industry, electrical material industry, vehicle, e.g.,automotive vehicle material industry, fiber material industry andutensil industry.

These resins are however accompanied by the drawback that they areextremely flammable. Keeping step with their extensive use, there is thesignificantly increasing tendency that they become a predominant causein fires. A high standard has hence been imposed on the safety of theseindustrial materials. It is therefore desired to improve these resins'properties such as flame retardancy and heat resistance.

Further, these resins also tend to undergo deterioration under heat,light or the like. It is therefore desired to improve the thermalstability of the resins and also to improve or impart other propertieswithout impairing the inherent good properties of these resins. It is anextremely important assignment to the industry to modify such resins andalso to develop new materials.

Flame Retardancy

With a view to improving the flame retardancy of such resins, a varietyof methods has been proposed to date. Known methods include, forexample, addition of a flame retardant, mixing with a flame-retardantresin, use of a flame-retardancy-imparting material (monomer) uponproduction of a resin to incorporate the material in the skeleton of theresin, and application of post treatment to a resin to impart flameretardancy. Among these methods, it is generally often practiced to adda flame retardant to a resin. Known examples of such a flame retardantinclude halogen-containing compounds, phosphorus-containing compounds,inorganic compounds and nitrogen-containing compounds.

Of these known flame retardants, use of a halogen-containing compoundgenerally results in poor heat resistance. Halogen-containing flameretardants are accompanied by such drawbacks that they are prone tosublimation, bleeding and/or the like, can hardly exhibit their effectsin many instances unless used in combination with antimony trioxide, andgive off an extremely noxious halogen-containing gas in a large volumein a fire. Use of a phosphorus-containing compound involves such defectsthat its effects are small when used singly, it can hardly exhibiteffects for certain types of resins, and it is often used in combinationwith a halogen-containing compound to develop the above-describeddrawbacks of the halogen-containing compound. Use of an inorganiccompound, on the other hand, is accompanied by the drawbacks that it maybe a rare natural resource like antimony trioxide and hence involvesproblems in availability, price and the like or that it may not showsignificant effects like aluminum hydroxide and must hence be added in alarge amount, thereby developing problems such as an increase inspecific gravity, reductions in physical properties and formability and,due to water contained therein, a deterioration in heat resistance.Further, use of a nitrogen-containing compound involves problems suchthat, as typified by the melamine type, it is susceptible tosublimation, bleeding and the like, its flame-retarding effects aresmall due to sublimation or the like when heated, and its price is highdue to difficulties in production. The flame-retarding method forresins, in which one or more of these known flame retardants areincorporated, is still insufficient for practical use, and substantiallimitations are imposed thereon both technically and economically.

With a view to overcoming the above-described drawbacks or problems insuch flame-retarding methods for resins, the present inventors haveconducted an extensive investigation. As a result, it has been foundthat the flame retardancy of such resins can be substantially improvedby incorporating therein one or more of particular novel diguanaminesdifferent in structure and properties from the conventionally knowncompounds. It has also been found that these diguanamines have betterheat resistance than melamines, sublimitation, bleeding and/or the likeis not observed, formation of char is excellent, and sagging or drippingof oil droplets or melt is substantially minimized, thereby making itpossible to provide an excellent method for making resins retardant toflame. Further, it has also been found that combined use of one or moreof the above-described diguanamines with phosphoruses, isocyanuricacids, cyanuric acids or amino-containing compounds can provide aflame-retarding method for resins, which can impart still improved flameretardancy to the resins. These findings have led to the presentinvention.

Heat Stabilization

Further, such resins are prone to embrittlement and/or coloration uponapplication of heat, light or another external energy thereto and/or inthe presence of oxygen or a heavy metal. This problem has thereforeimposed limitations on their use in a wide variety of fields despitetheir excellent properties. With a view to improving the above problems,various proposals have been made to date. These proposals, however, arestill insufficient to overcome these problems. In some extreme cases,the inherent excellent properties of resins are lost. Such proposals aretherefore by no means suited for practical use.

As a specific example of such conventional thermal stabilizationmethods, there is disclosed a method for thermally stabilizing a resinby incorporating, for example, a thermal stabilizer such as a benzoate,amine, arylphosphonic diamide or organic phosphite. To impartpractically satisfactory stability to heat, light and the like, nomethod has however been developed yet.

It is also known to thermally stabilize a resin by incorporating thereinmelamine, acetoguanamine, benzoguanamine or the like. This method ishowever accompanied by the drawbacks that it shows no specific effect onthe improvement of stability to heat, light and the like and is unableto bring about any sufficient effects from the practical viewpoint.

Known thermal stabilization methods for resins also includeincorporation of phthaloguanamine, spirogunamine or the like. Thismethod is however accompanied by problems such that these compounds areinferior in ultraviolet light resistance, weatherability and the likeand undergo substantial discoloration or the like and, when molded orotherwise formed at high temperatures, resins are substantially coloredor discolored, the resultant resins do not have sufficient thermalstability, and such thermal stabilizers themselves are subjected tothermal decomposition during processing, molding and the like. Thesethermal stabilization methods for resins are accordingly insufficientfor practical use and are accompanied by substantial limitations in bothtechnology and economy.

In view of the above-described drawbacks or problems of such thermalstabilization methods for resins, the present inventors have proceededwith an extensive investigation. As a result, it has been found thatincorporation of a specific novel diguanamine different in structure andproperties from the above-described compounds in a resin cansignificantly improve its ultraviolet light resistance, weatherabilityand thermal stability, can minimize coloration or discoloration whenperforming processing, molding or the like at high temperatures, and canreduce deterioration even during use for a long time at relatively hightemperatures. It has also been found the thermal stabilizer itself isresistant to decomposition even at high temperatures can hence provide athermal stabilization method for the provision of a resin excellent inhandling ease and the maintenance of properties. These findings have ledto the present invention.

Compatibilization

In addition, such resins have excellent properties and are used in awide variety of industrial fields. As methods for improving variousproperties of such resins or modifying such resins to impart a newproperty thereto without impairing their inherent good properties,various polymer alloying methods have been proposed.

As such polymer alloying methods for resins, it has conventionally beenproposed, for example, to modify the resins themselves or to add a thirdcomponent such as a compatibilizing agent to them. However, substantialtechnical and/or economical limitations are imposed on the former methodbecause of the need for a difficult reaction and cumbersome steps forthe modification of each resin, reductions in properties such as amolecular weight reduction of the resin upon modification, etc. Thelatter method, on the other hand, is accompanied by drawbacks such thatproperties of each resin, such as heat resistance, weatherability andwater resistance, are reduced by the inclusion of the third component,preparation of the compatibilizing agent requires a complex process, andhigh production cost is needed.

With a view to overcoming the above-described drawbacks or problems ofsuch compatibilization methods for resins, the present inventors haveconducted with an extensive investigation. As a result, it has beenfound that incorporation of a particular novel diguanamine, which isdifferent in structure and properties from conventionally knowncompounds, in a blend of two or more resins can provide acompatibilization method for resins. According to the compatibilizationmethod, excellent compatibilization can be achieved between differentkinds of resins, and the resin so obtained has superb melt propertiesand excellent heat resistance, weatherability and water resistance.Moreover, the compatibilizing agent can be easily produced. Thecompatibilization method also benefits low production cost. The abovefinding has led to the present invention.

Diguanamine Derivative

Further, this invention also provides a diguanamine derivative, which isan N-substituted derivative of the above-described diguanamine, itspreparation process and its application.

N-substituted melamines available from melamine, benzoguanamine and thelike are known. Their preparation processes are also known. SuchN-substituted melamines include various hydroxyl-containing melaminederivatives which have been provided for the usefulness. Known examplesinclude N-polyoxalkyl-substituted melamines obtained by an additionreaction of melamine with epoxides as well as N-hydroxyalkyl-substitutedmelamines obtained by a reaction of melamine with aminoalkanols.

These N-substituted melamines are however accompanied by drawbacks suchthat they cannot impart practically sufficient flame retardancy, heatresistance and mechanical properties (e.g., flexibility and toughness)when used as resin raw materials, resin modifiers or the like and,because they do not contain many functional groups, they can hardlyexhibit sufficient effects as modifiers, chain extenders, curing agents,crosslinking agents or the like.

Further, in the former process for the preparation of anN-polyoxalkyl-substituted melamine, the yield is extremely low when thereaction is conducted in the absence of a solvent. Even when a solventsuch as dimethyl sulfoxide, which has better melamine dissolving abilitythan other solvents, is used, it is difficult to allow the reaction tosmoothly proceed because its melamine dissolving ability is stillinsufficient even at high temperatures. It is hence difficult to obtainthe target product. Instead, products having high molecular weights onlyare obtained, thereby making it difficult to obtain a product having adesired molecular weight or having a narrow molecular weightdistribution. Substantial limitations are therefore imposed on such areaction product in use, performance and the like. The latter processfor the preparation of an N-hydroxyalkyl-substituted melamine, on theother hand, is also accompanied by problems such that, due toinsufficient dissolution of the melamine and also the need forconducting the reaction at a high temperature even when the reaction iscarried out in the presence of a solvent, an excess amount of anaminoalkanol and the like, the reaction can hardly proceed uniformly andrequires a long time for the preparation, a desired product having anarrow molecular weight distribution can hardly be obtained, thereaction product is substantially colored, byproducts are formed inlarge amounts, and the purification and isolation become complex.

As has been described above, substantial technical and/or economicallimitations are imposed on the known N-substituted melamines upon useand preparation.

With a view to overcoming the above-described drawbacks or problems ofsuch N-substituted melamines, the present inventors have conducted anextensive investigation. As a result, the present inventors have founddiguanamine derivatives excellent in properties such as heat resistance,flame retardancy, weatherability, flexibility and toughness anddifferent in structure and properties from the conventional compounds aswell as novel hydroxyl-containing or oxalkyl-containing diguanaminederivatives which contain one or more active hydroxyl or imino groups orthe like capable of showing excellent reactivity to compounds containingvarious functional groups and permit selection of the number offunctional group(s) from a wide range up to those containing 8 activehydrogen atoms, leading to the present invention.

Further, the present inventors have found an excellent process for thepreparation of such diguanamine derivatives. According to the process,upon preparation of a diguanamine derivative, the target reactionproduct can be easily obtained in a high yield by reaction of a noveldiguanamine different in structure and properties from the conventionalcompounds with an amine HO--Y₉ --NH₂, Y₉, R₉ being a divalent groupcontaining at least two carbon atoms or by reaction of theabove-described diguanamine, a hydroxyl-containing diguanaminederivative and an epoxide.

It has also been found that incorporation of the above-describeddiguanamine derivative can provide an excellent method for making theresin retardant to flame. The diguanamine derivative has better heatresistance than melamine and the like, so that sublimation, bleeding orthe like is not observed. Formation of char is excellent so that saggingor dripping of oil droplets or a melt is significantly minimized. Theresulting resin has good melt properties. Further; its combined use witha phosphorus, an isocyanuric acid, cyanuric acid or an amino-containingcompound can provide still improved flame retardancy. These findingshave led to the present invention.

Moreover, it has also been found that incorporation of theabove-described diguanamine derivative and organic polyisocyanatecomponent can provide a polyurethane resin composition which can providea material excellent in properties such as flame retardancy, heatresistance, water resistance, abrasion resistance and elasticity,leading to the present invention.

Organic Microspheres

There are also known cured organic microspheres obtained by using andcuring an amino resin which has been obtained by reacting an aminocompound, such as urea, melamine, benzoguanamine orcyclohexanecarboguanamine, with formaldehyde.

Among such cured organic microspheres, those obtained using urea areaccompanied by drawbacks such as poor weatherability, especially poorsunlight fastness, unclear color and low impact resistance. Thoseobtained using melamine, on the other hand, are accompanied by drawbackssuch as poor impact resistance. Those obtained using benzoguanamine areexcellent in water resistance, but are accompanied by drawbacks suchthat their weatherability is very poor and they hence undergosubstantial discoloration in outdoor use. Further, those obtained usingcyclohexanecarboguanamine are excellent in weatherability but areaccompanied by drawbacks such that they are still insufficient in heatresistance, impact resistance, abrasion resistance, solvent resistanceand the like.

As a method for obtaining cured organic microspheres in a colored form,it is known to color a polymer with a colorant such as a dye or pigmentand then to finely grind the polymer so colored. Such a method isaccompanied by drawbacks such as difficulties in controlling the spheresize upon fine grinding and high grinding cost. In addition, it isnecessary to control the low crosslinking degree and molecular weight ofthe resin upon production of the resin so that its fine grinding can befacilitated. This however leads to problems such as insufficient impactresistance, solvent resistance and heat resistance.

With a view to overcoming the above-described drawbacks of such curedorganic microspheres, the present inventor have carried out an extensiveinvestigation. As a result, it has been found that polymericmicrospheres excellent in heat resistance, solvent resistance,weatherability, impact resistance, abrasion resistance and the like canbe furnished by emulsifying an amino resin, which has been obtained byreacting an amino compound with an aldehyde, said amino compoundincluding a novel particular diguanamine different in structure andproperties from the above-described compounds, adding a curing agent tothe amino resin and then polymerizing the amino resin. It has also beenfound that polymeric microspheres useful as a resinous colorantexcellent in weatherability, color, solvent resistance, impactresistance and the like can be furnished by coloring the amino resins sopolymerized. The above findings have led to the present invention.

As has been described above, it is an industrially important assignmentto improve the flame retardancy of resins. The present inventors havefound that an excellent flame-retarding method can be provided for eachresin by incorporating therein novel polymeric microspheres according tothe present invention. The novel polymeric microspheres cansignificantly improve the flame retardancy of the resin. Theabove-described novel diguanamine is free from sublimation, bleeding orthe like. The resin so obtained is excellent in the formation of char sothat sagging or dripping of oil droplets or melt can be minimized.Further, production of noxious gas can also be minimized. These findingshave led to the present invention.

DISCLOSURE OF THE INVENTION

In one aspect of the present invention, there is thus provided a methodfor making a resin retardant to flame, which comprises incorporating3-50 wt. %, based on said resin, of at least one diguanamine selectedfrom diguanamines represented by the formula (1) or by the formula (2).

In another aspect of the present invention, there is also provided amethod for thermally stabilizing a resin, which comprises incorporating0.01-5 wt. %, based on said resin, of at least one diguanamine selectedfrom the diguanamines represented by the formula (1) or (2).

In a further aspect of the present invention, there is also provided amethod for making a resin compatible, which comprises incorporating atleast one diguanamine, which is selected from the diguanaminesrepresented by the formula (1) or (2), in a blend of at least two resinsincluding at least one resin selected from polyamide resins,polyphenylene ether resin, polyimide resins and polyaramid resins.

In still further aspects of the present invention, there are alsoprovided a diguanamine derivative, a process for the preparation of thediguanamine derivative, and flame-retarding, thermal stabilization andcompatibilization methods for a resin, said methods all making use ofthe diguanamine derivative, as well as polymeric microspheres using theabove-described diguanamine and a flame-retarding method for a resin,said method making use of the polymeric microspheres.

BEST MODE FOR CARRYING OUT THE INVENTION Flame-retarding Method

In the flame-retarding method according to this invention for the resin,the diguanamine can be used in an amount of 3-50 wt. %, preferably 4-40wt. % based on the resin. Amounts smaller than 3 wt. % can hardly bringabout sufficient effects for the improvement of flame retardancy, butamounts greater than 50 wt. % can lead to reductions in physicalproperties as the resulting compositions can have poor formability orthe resin can be deteriorated. Amounts outside the above range aretherefore not preferred.

In the above-described flame-retarding method for the resin, use ofphosphoruses selected from the group consisting of simple substances ofphosphorus and phosphorus-containing compounds in combination with thediguanamine of this invention in the resin is particularly preferredbecause they can impart the synergistic effect that the flame-retardingeffects can be improved further. Such excellent synergistic effects arebelieved to be produced for their functions not only to facilitateformation of a flame retardant film of relatively low volatility on aburning resin surface but also to further promote formation of char andhence to increase a layer of char so that oxygen can be prevented fromspreading to the burning surface, release of flammable gas from theresin portion can be reduced and conduction of heat to the resin portioncan be reduced.

Useful examples of such phosphoruses include, but are not limited to,simple substances of phosphorus such as red phosphorus;phosphorus-containing acids such as phosphoric acid, polyphosphoricacids, phosphorous acid, phosphonic acid, phosphate salts, polyphosphatesalts, phosphite salts and phosphonate salts; phosphate esters such asphosphoric triesters, polyphosphate esters, acidic phosphate esters, andsalts thereof; phosphite esters such as phosphorous triesters andphosphorous diesters; phosphonate esters such as phosphonate esters,acidic phosphonate esters and salts thereof; phosphines such asphosphine, phosphine oxide and phosphonium salts; and sulfur-containingphosphorus compounds such as dialkyl thiophosphates and salts thereof.

Illustrative examples of such phosphorus-containing acids include acidssuch as phosphoric acid, pyrophosphoric acid, tripolyphosphoric acid,polyphosphoric acid, phosphorous acid and phosphonic acid; and saltsavailable by either partially or fully neutralizing such acids withbases such as ammonia, amines, alkali metals or alkaline earth metals,namely, ammonium phosphate, ethylenediamine phosphate, sodium phosphate,calcium phosphate, melamine pyrophosphate, sodium pyrophosphate,ammonium tripolyphosphate, sodium tripolyphosphate, ammoniumpolyphosphates, sodium polyphosphates, ammonium phosphite, calciumphosphite and ammonium phosphonate. Of these, ammonium polyphosphatesrepresented by formula (NH₄)_(n+2) P_(n) O_(3n+1) wherein n stands foran integer greater than 5 are preferred. It is however to be noted thatthe present invention is not necessarily limited to the use of suchillustrative examples.

In the above-described ammonium polyphosphates represented by formula(NH₄)_(n+2) P_(n) O_(3n+1) wherein n stands for an integer greater than5, it is preferred to set n at a substantially large value to make watersolubility smaller in view of flame retarding effects and the physicalproperties of the resulting composition. A salt in which n is an integergreater than 50 is particularly preferred. This salt practicallycorresponds to a metaphosphate, (NH₄ PO₃)_(n).

Examples of such ammonium polyphosphates include "Exolit 263" (tradename; product of Hoechst AG), "Exolit 422" (trade name; product ofHoechst AG) and "Phoscheck P/30" (trade name; product of MonsantoChemical Company).

Illustrative of such phosphate esters include, but are not to be limitedto, phosphoric triesters such as trimethyl phosphate, triethylphosphate, tri-n-butyl phosphate, trioctyl phosphate, trilaurylphosphate, tricetyl phosphate, tristearyl phosphate, trioleyl phosphate,tris(butoxyethyl) phosphate, triphenyl phosphate, tricresyl phosphate,trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenylphosphate, tris(isopropylphenyl) phosphate, ethyl diphenyl phosphate,isopropyl diphenyl phosphate, n-butyl diphenyl phosphate, 2-ethylhexyldiphenyl phosphate, isodecyl diphenyl phosphate, cetyl diphenylphosphate, stearyl diphenyl phosphate, oleyl diphenyl phosphate, butyldicresyl phosphate, octyl dicresyl phosphate, lauryl dicresyl phosphate,diphenyl 2-metacroyloxyethyl phosphate, tris(2-chloroethyl) phosphate,tris(2-chloropropyl) phosphate, tris(2,3-dichloropropyl) phosphate, andtris(2,3-dibromopropyl) phosphate, tris(bromochloropropyl)phosphate,tris(tribromophenyl)phosphate; acidic phosphate esters such as(mono,di)methyl acid phosphate (mixture), (mono,di)ethylacid phosphatemixture, diisopropylacid phosphate, monobutyl acid phosphate, dibutylacid phosphate, di-2-ethylhexyl phosphate, monoisodecyl acid phosphate,(mono,di)lauryl acid phosphate (mixture), (mono,di)tridecyl acidphosphate (mixture), (mono,di)stearyl acid phosphate (mixture),(mono,di)oleyl acid phosphate (mixture), (mono,di)2-chloroethyl acidphosphate (mixture, (mono,di)butoxyethyl acid phosphate (mixture),ethylene glycol acid phosphate, dibutyl pyrrophosphate, monophenyl acidphosphate, diphenyl acid phosphate, monocresyl acid phosphate, dicresylacid phosphate, monoxylenyl acid phosphate, and dixylenyl acidphosphate; and ammonia, amine, melamine, alkali metal and alkaline earthmetal salts of acidic phosphate esters, such as ammonium dimethylphosphate, ammonium diethyl phosphate, ammonium ethyl phosphate,ammonium di-n-butyl phosphate, triethanolamine dibutoxyethyl phosphate,morpholine dioctyl phosphate, sodium mono-n-butyl phosphate, ammoniumdiphenyl phosphate, melamine diphenyl phosphate, piperazine diphenylphosphate, ammonium phenyl phosphate, ethylenediamine dicresylphosphate, sodium cresyl phosphate, and melamine dixylenyl phosphate.

Examples of such phosphite esters include, but are not limited to,phosphite triesters such as trimethyl phosphite, triethyl phosphite,tributyl phosphite, tris(2-ethylhexyl) phosphite, tridecyl phosphite,trilauryl phosphite, trioleyl phosphite, tristearyl phosphite, triphenylphosphite, tris(nonylphenyl) phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(dinonylphenyl) phosphite, bis(nonylphenyl) dinonylphenylphosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl monodecylphosphite, diphenyl mono(tridecyl) phosphite, phenyl diisooctylphosphite, tetraphenyl dipropylene glycol diphosphite, poly(dipropyleneglycol) phenyl phosphite, diisodecyl pentaerythritol diphosphite,bis(tridecyl) pentaerythritol diphosphite, distearyl pentaerythritoldiphosphite, bis(nonylphenyl) pentaerythritol diphosphite,bis(2,4-di-t-butylphenyl) pentaerythritol diphosphite, phenyl4,4'-isopropylidenediphenyl pentaerythritol diphosphite, tetraphenyltetra(tridecyl) pentaerythritol tetraphosphite,tetra(tridecyl)-4,4'-isopropylidenediphenyl phosphite, hydrogenatedbisphenol A phosphite polymer, pentaerythritol hydrogenated bisphenol Atriphenyl phosphite polycondensate, tetra(tridecyl)-4,4'-n-butylidenebis(2-t-butyl-5-methylphenol) diphosphite, bis(neopentyl glycol)1,4-cyclohexane dimethylene phosphite, bis(octylphenyl)bis[4,4'-n-butylidene bis(2-t-butyl-5-methylphenol)] 1,6-hexanediolphosphite, andtetra(tridecyl)-1,1,3-tris(2'-methyl-5'-t-butyl-4'-oxyphenyl)butanediphosphite; and phosphite diesters such as dimethyl hydrogenphosphite,dibutyl hydrogenphosphite, di(2-ethylhexyl) hydrogenphosphite, dibutylhydrogenphosphite, dilauryl hydrogenphosphite, dioleylhydrogenphosphite, and diphenyl hydrogenphosphite.

Examples of such phosphonic acids include, but are not limited to,phosphonate diesters such as dimethyl methylphosphonate, ethyldiethylphosphonoacetate, bis(2-chloroethyl) vinylphosphonate, diethylN,N-bis(2-hydroxyethyl)aminomethylphosphonate, dibutyl butylphosphonate,di-2-ethylhexyl hydroxymethylphosphonate, di-2-ethylhexyl2-ethylhexylphosphonate, dimethyl phenylphosphonate, diethylphenylphosphonate, diallyl phenylphosphonate, dioctyl phenylphosphonate,and dinaphthyl phenylphosphonate; acidic phosphonate esters such asmono-2-ethylhexyl 2-ethylhexylphosphonate and monooctylphenylphosphonate; and phosphonate ester salts such as ammoniummono-2-ethylhexyl 2-ethylhexylphosphonate, triethanolamine monooctylphenylphosphonate, melamine mono-2-ethylhexyl 2-ethylhexylphosphonate,and sodium monooctyl phenylphosphonate.

Examples of such phosphines include, but are not limited to, phosphinessuch as triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine,tri-n-hexylphosphine, tri-n-octylphosphine, tris(2-cyanoethyl)phosphine,tris (3-hydroxypropyl)phosphine, tricyclohexylphosphine,dicyclohexylphosphine, triphenylphosphine, tri-p-tolylphosphine,tri(2,6-dimethoxyphenyl)phosphine, 9-phosphabicyclo[3.3.1],[4.2.1]nonane (mixture), bis(1,2-diphenylphosphino)ethane,bis(1,4-diphenylphosphino)butane, diphenyl-p-styrylphosphine,diphenylphosphinous chloride, and bis (diphenylphosphino)ferrocene;phosphine oxides such as triethylphosphine oxide, tri-n-propylphosphineoxide, tri-n-butylphosphine oxide, tri-n-hexylphosphine oxide,tri-n-octylphosphine oxide, tris(2-cyanoethyl)phosphine oxide,tris(3-carboxyethyl)phosphine oxide, tris(3-hydroxypropyl)phosphineoxide, and triphenylphosphine oxide; and phosphonium salts such astetra-n-butylphosphonium bromide, tri-n-butylallylphosphonium bromide,ethylenebistris(2-cyanoethyl)phosphonium bromide,ethyltriphenylphosphonium bromide, tetraphenylphosphonium bromide,tri-n-octylethylphosphonium bromide, tetra-n-butylphosphoniumO,O-diethylphosphorodithioate, tetrakis(hydroxymethyl)phosphoniumsulfate, tetra-n-butylphosphonium iodide, ethyltriphenylphosphoniumiodide, triethylbenzylphosphonium chloride, tetra-n-butylphosphoniumchloride, tri-n-butyltetradecylphosphonium chloride,tri-n-butylhexadecylphosphonium chloride,tris(2-cyanoethyl)allylphosphonium chloride, benzyltriphenylphosphoniumchloride, and bis(triphenylphosphin)iminium chloride.

Examples of such sulfur-containing phosphorus compounds include, but arenot limited to, dimethyl phosphorodithioate, diethyl phosphorodithioate,di-n-propyl phosphorodithioate, ammonium diethyl phosphorodithioate,melamine di-n-propyl phosphorodithioate, sodium dimethylphosphorodithioate, trilauryl trithiophosphite, tris(lauryl-2-thioethyl)phosphite, diphenyl bis[4,4'-n-butylidene bis(2-t-butyl-5-methylphenyl)]thiodiethanol diphosphite, triphenylphosphine sulfide,tris(2-cyanoethyl)phosphine sulfide, and tri-n-butylphosphine sulfide.

In the present invention, such phosphoruses can be used in an amount of5-40 wt. %, preferably 10-30 wt. % based on such resins. Amounts smallerthan 5 wt. % cannot bring about sufficient synergistic effects forimproving the flame retardancy. Amounts greater than 40%, on the otherhand, cause deteriorations in physical properties. Because of thesedisadvantages, amounts outside the above range are not preferredpractically.

In such resins, the phosphoruses may be present separately fromcomponents such as the diguanamine or a part or the entire part of thephosphoruses may form a salt with the diguanamine according to thepresent invention. Inclusion of a salt, for example, in the form of asalt of phosphoric acid, a polyphosphoric acid, phosphorous acid,phosphonic acid, acidic ammonium polyphosphate, an acidic phosphateester or an acidic phosphonate ester with the diguanamine is preferredbecause of still better synergistic effects for the improvement of flameretardancy.

The diguanamine according to the present invention can improve the flameretardancy of such a resin further when incorporated together with aparticular isocyanuric acids and/or cyanuric acids in the resin as amethod for making the resin retardant to flame. This combined use istherefore preferred.

Illustrative of such particular isocyanuric acids and cyanuric acidsinclude isocyanuric acids represented by the following formula (9):##STR12## wherein X₂, X₃ and X₄ may be the same or different andindividually represent a hydrogen atom or a C₁₋₃ alkyl, C₁₋₃ alkyloxy,phenyl or glycidyl group, and cyanuric acids represented by thefollowing formula (10): ##STR13## wherein X₂, X₃ and X₄ have the samemeanings as defined in formula (9).

The isocyanuric acids useful in the practice of the present inventionare compounds represented by the formula (9) in which X₂, X₃ and X₄ arethe same or different and individually represent a substituent selectedfrom the group consisting of a hydrogen atom, C₁₋₃ alkyl groups, C₁₋₃oxyalkyl group, a phenyl group and a glycidyl group. Specific examplesof such isocyanuric acids include, but are not limited to, isocyanuricacid, methyl isocyanurate, trimethyl isocyanurate, triethylisocyanurate, tris(2-hydroxyethyl) isocyanurate, phenyl isocyanurate,diphenyl isocyanurate, triphenyl isocyanurate, dimethyl phenylisocyanurate and triglycidyl isocyanurate.

The cyanuric acids useful in the practice of the present invention arecompounds represented by the formula (10) in which X₂, X₃ and X₄ havethe same meanings as defined in formula (9). Specific examples of suchcyanuric acids include, but are not limited to, cyanuric acid, methylcyanurate, trimethyl cyanurate, triethyl cyanurate, tris(2-hydroxyethyl)cyanurate, phenyl cyanurate, diphenyl cyanurate, triphenyl cyanurate,dimethyl phenyl cyanurate, and triglycidyl cyanurate.

In the present invention, the molar ratio of the sum of the isocyanuricacids and the cyanuric acids to the diguanamine can range from 0.02 to10, preferably from 0.1 to 5. Molar ratios smaller than 0.02 are toosmall to sufficiently bring about effects of their combined use, whereasmolar ratios greater than 10 lead to reductions in physical properties.Molar ratios outside the above range are therefore not preferred fromthe practical viewpoint.

In the resin, such isocyanuric acids and cyanuric acids may presentseparately from components such as the diguanamine, or a part or theentire part of these acids may form salts and/or react with thediguanamine according to the present invention and may hence becontained partially or entirely in the form of salts. Inclusion of asalt and/or product, for example, a salt of an isocyanuric acid with thediguanamine and a reaction product of triglycidyl cyanurate with thediguanamine can bring about still better flame-retarding effects, heatresistance and the like and is hence preferred.

Useful examples of such a salt include, but are not limited to, a saltobtained by dissolving or dispersing the isocyanuric acid and thediguanamine in a solvent and heating the resulting solution to reactthem, a salt obtained by reacting the isocyanuric acid with thediguanamine at a molar ratio of from 1 to several, and mixtures of saltsformed through these reactions.

Further, the diguanamine according to the present invention can improvethe flame retardancy of a resin further when employed in accordance witha flame-retarding method for the resin in which the diguanamine isincorporated together with an amino-containing compound in the resin.This combined use of the diguanamine with the amino-containing compoundis therefore preferred.

The amino-containing compound contains at least one aliphatic group,alicyclic group, aromatic group or heterocyclic group having at leasttwo carbons. Preferred are those containing at least one aliphaticgroup, alicyclic group or heterocyclic group having at least twocarbons. More preferred are compounds which contain at least one1,2-ethanediamino group (>N--CH₂ CH₂ --N<), cyclohexylamino group##STR14## piperidino group ##STR15## piperadinyl group ##STR16##morpholino group ##STR17## amido bond ##STR18## or urea bond ##STR19##as well as dicyandiamide, guanidine, and reaction products between suchcompounds and aldehydes such as formaldehyde or epoxy compounds.

Specific examples of such amino-containing compounds include, but arenot limited to, 1,2-ethylenediamine, 1,3-diaminopropane,1,2-diaminopropane, 1,4-butylenediamine, 1,6-hexamethylenediamine,polyalkylenepolyamine such as diethylenetriamine, triethylenetetramine,tetraethylenepentamine and pentaethylenehexamine, cyclohexylamine,cyclohexyldiamine, 1,3-bis(aminomethyl)cyclohexane, aniline,benzylamine, furfurylamine, N-(3-aminopropyl)morpholine,N-(2-aminoethyl)morpholine, N-(2-aminoethyl)piperazine,N-(3-aminopropyl)piperazine, N-(2-aminoethyl)piperidine,N,N'-bis(2-aminoethyl)piperazine, dicyandiamide, guanidine, urea, andpolyamide resins; and reaction products between these compounds andaldehydes such as formaldehyde, for example, ethylenediamineformaldehyde(1/1) reaction product, piperazineformaldehyde (1/1) reaction product,pentamethylenehexamine, and salts thereof.

In the present invention, the amino-containing compound can be used inan amount of 0.01-10 wt. %, preferably 0.05-5 wt. % based on the resin.Amounts smaller than 0.01 wt. % cannot exhibit synergistic effects tosufficient extent for the improvement of flame retardancy, whereasamounts greater than 10 wt. % lead to reductions in physical properties.Amounts outside the above range are therefore not preferred from thepractical viewpoint.

Illustrative examples of resins to which the present invention can beapplied include synthetic resins and oils, for example, thermoplasticresins, thermosetting resins and rubbers as well as modified resins suchas blends, block copolymers, graft copolymers and rubber-modifiedpolymers of such resins and/or rubbers.

Specific examples of such resins include, but are not limited to,thermoplastic resins, for example, styrene resins such as polystyrene,co- and terpolymers between styrene and other monomers [e.g., maleicanhydride, α-methylstyrene, butadiene, acrylonitrile, and (meth)acrylateesters], rubber-modified polystyrenes, rubber-modifiedstyreneacrylonitrile copolymers and rubber-modified styrenemaleicanhydride copolymers, polyolefin resins such as polyethylene,polypropylene, polybutylene, poly-3-methylbutene, ethylene-vinyl acetatecopolymers, ethylene-propylene copolymers and EPDMs(ethylene-propylene-diene terpolymers), (meth)acrylic resins such aspolymethyl acrylate and polymethyl methacrylate, polyamide resins suchas nylon 4, nylon 6, nylon 11, nylon 12, nylon 46, nylon 66, nylon 610,nylon 612 and copolymerized nylons, saturated polyester resins such aspolyethylene terephthalate and polybutylene terephthalate, polyphenyleneether resins such as poly(2,6-dimethyl-1,4-phenylene) ether,poly(2-methyl-6-ethyl- 1,4-phenylene) ether,poly(2,6-diethyl-1,4-phenylene) ether,poly(2,6-di-n-propyl-1,4-phenylene) ether,poly(2-methyl-6-n-butyl-1,4-phenylene) ether,poly(2-methyl-6-chloro-1,4-phenylene) ether,poly(2-methyl-6-hydroxyethyl-1,4-phenylene) ether,poly(2-methyl-6-chloroethylene-1,4-phenylene) ether and2,6-dimethylphenol-2,3,6-trimethylphenol copolymers, end-cappedpolyphenylene ethers thereof and resins obtained by modifying suchpolyphenylene ether resins with such as styrene resin and polyamideresin, polyacetal resins such as polyoxymethylene and polymerscontaining oxymethylene units and other units (for example, succinicanhydride, n-dodecenylsuccinic anhydride, methylsuccinic anhydride,tetrapropylsuccinic anhydride, maleic anhydride, phthalic anhydride,hexahydrophthalic anhydride, itaconic anhydride, β-hydroxypropylenegroup, oxyalkylene groups); halogenated resins such as polyvinylchloride, polyvinylidene chloride, chlorinated polyethylene, chlorinatedpolypropylene, chlorinated rubber, co- and ter-polymers between vinylchloride and other monomers [e.g., vinyl acetate, ethylene, propylene,styrene, isobutylene, vinylidene chloride, maleic anhydride,acrylonitrile, butadiene, isoprene, chlorinated propylene, and(meth)acrylate esters], polyvinyl bromide, brominated polyethylene,polyvinyl fluoride, polyvinylidene fluoride and fluorinated resins,vinyl acetate resin, polyamide-imides, polyimide resins,polyether-imides, polyphenylene-sulfide resins, polyether-sulfones,polysulfone resins, polyamine-sulfones, polycarbonate resins, liquidcrystal (polyester) polymers, cyclic polyolefins, polyetheretherketones,polyarylates, phenoxy resins, silicone resins, blends, block copolymers,graft copolymers and rubber-modified polymers of these resins;thermosetting resins, for example, unsaturated polyester resins such asdiallyl phthalate resins (e.g. polydiallyl phthalate, polydiallylterephthalate and polydiallyl 2,6-naphthalenedicarboxylate) andmaleic-acid-(fumaric acid)-containing polyester-styrene resins, urethaneresins, epoxy resins, silicone resins, phenol resins, furan resins,amino resins, blends thereof and resins obtained by modifying theseresins with rubber or the like; rubbers such as synthetic rubbers andvulcanized rubbers; and blends and modified resins of these resins andoils such as lubricating oils, silicone oils, metal working oils andpolypropylene wax.

These resins can each be used in an amount of 50-98 wt. %, preferably65-96 wt. % based on a corresponding resin composition obtained inaccordance with the flame-retarding method of the present invention. Ifthe amount of the resin exceeds 98 wt. %, flame-retarding effects becomesmaller. An amount smaller than 50 wt. %, on the other hand, results ina composition having poor formability or reduced physical properties dueto deterioration or the like of the resin. Amounts outside the aboverange are therefore not preferred.

In the flame-retarding method of the present invention for resins, thethermal stability and the like of such resins can be improved byadditionally incorporating additives such as phenolic antioxidants,amine-base antioxidants, sulfur-containing antioxidants and lightstabilizers. These additives can be chosen as needed depending on theapplication purpose.

Illustrative of such phenolic antioxidants include3-methyl-4-isopropylphenol, 2,6-di-t-butylphenol,2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butyl-4-methylphenol,2,4-dimethyl-6-(2-methylcyclohexyl)phenol, 2,5-di-t-butylhydroquinone,3-t-butyl-4-hydroxyanisole, styrenated phenol, hydroquinone monobenzylether, 2,5-diamylhydroquinone, 2,6-di-t-butyl-4-methoxyphenol,4-hydroxymethyl-2,6-di-t-butyl phenol,2,6-di-t-butyl-α-dimethylamino-p-cresol, 4-(N-stearoylamino)phenol,4,4'-dihydroxydiphenyl, 4,4'-bis(2,6-di-t-butylphenol),2,2'-methylene-bis-(4-methyl-6-t-butylphenol),2,2'-methylene-bis-(4-ethyl-6-t-butylphenol),4,4'-methylene-bis-(2-methyl-6-t-butylphenol),4,4'-methylene-bis-(2,6-di-t-butylphenol),2,2'-dihydroxy-3,3'-bis-(2-methylcyclohexyl)-5,5'-dimethyl-diphenylmethane,1,1-bis-(4-hydroxyphenyl)-cyclohexane,4,4'-cyclohexilidene-bis-(2-cyclohexylphenol),4,4'-butylidene-bis-(3-methyl-6-t-butylphenol), octadecyl3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, triethylene glycolbis-[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediolbis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], pentaerystyryltetrakis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], ethyl3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,2,6-bis(2-hydroxy-3-t-butyl-5-methylbenzyl)-4-methylphenol,1,1,3-tris-(2-methyl-4-hydroxy-5-t-butylphenyl)-butane,1,3,5-tris-(3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,dioctadecyl 2-(3-methyl-4-hydroxy-5-t-butylbenzyl)malonate, didodecyl4,4-thiobis-(2-methyl-6-t-butylphenyl)malonate,bis-(2-hydroxy-3,5-di-t-butylphenyl)sulfide,4,4'-thio-bis-(3-methyl-6-t-butylphenol),1,1-bis-(2-methyl-4-hydroxy-5-t-butylphenyl)-3-dodecylmercapto-butane,octadecyl S-(3,5-dimethyl-4-hydroxyphenyl)-thioglycolate,2,2'-thio-bis-(4-methyl-6-t-butylphenol), dimethyl4-hydroxy-3,5-di-t-butylbenzylphosphonate, diethyl4-hydroxy-3,5-t-butylbenzylphosphonate, dioctadecyl4-hydroxy-3,5-di-t-butylbenzylphosphonate,tris-(3,5-di-t-butyl-4-hydroxyphenyl) phosphate,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]-octane-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,2,4-bis-(octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-s-triazine,2,4-bis-(3,5-di-t-butyl-4-hydroxyphenoxy)-6-octyl-s-triazine,1,3,5-tris-(3,5-di-t-butyl-4-hydroxyhydrocinnamoyl)hexahydro-s-triazine,tris(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate,tris[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl] isocyanurate,N,N'-hexamethylenebis-(3,5-di-t-butyl-4-hydroxy-hydrocinnamide),2-t-butyl-6-(3'-t-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenylacrylate, 2,2'-oxamido-bis[ethyl3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],3,9-bis(1,1-dimethyl-2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl)-2,4,8,10-tetraoxapyro[5.5]undecane.They can each be used in an amount of 0.001-2.0 wt. %, preferably0.05-1.0 wt. % based on the resin.

Exemplary amine-base antioxidants include phenyl-1-naphthylamine,phenyl-2-naphthylamine, N,N'-diphenyl-p-phenylenediamine,N,N'-di-2-naphthyl-p-phenylenediamine,N,N'-di-sec-butyl-p-phenylenediamine,6-ethoxy-2,2,4-trimethyl-1,2-dihydroxyquinoline, 6-dodecyl-2,2,4-trimethyl-1,2-dihydroxyquinoline, dioctyliminodibenzyl,diethanolamine, diisopropanolamine, dibutanolamine, triethanolamine,triisopropanolamine, tributanolamine, dodecylethanolamine,octadecyldiethanolamine, N,N'-diphenylethylenediamine,triethyltetramine, 7 mole ethylene oxide adduct of dodecylamine, 4 moleethylene oxide adduct of tridecylamine, 10 mole ethylene oxide adduct ofoctadecylamine, and 20 mole ethylene oxide adduct of hexadecylamine.They can each be used in an amount of 0.02-5.0 wt. % based on the resin.

Examples of such sulfur-containing antioxidants include diethyl3,3'-thio-di-propionate, dilauryl 3,3'-thio-di-propionate, ditridecyl3,3'-thio-di-propionate, dimyristyl 3,3'-thio-di-propionate, distearyl3,3'-thio-di-propionate, 2-methylmercaptobenzoimidazole, stearyl(3,5-dimethyl-4-oxybenzyl)thioglycolate, diphenyl thiourea,thiodipropionic acid, phenothiazine and pentaerythritoltetrakis-(β-lauryl thiopropionate). They can be used in an amount of0.01-4.0 wt. %, preferably 0.05-2.0 wt. % based on the resin.

Illustrative of such light stabilizers include, but are not limited to,benzophenone compounds such as benzophenone,2-hydroxy-4-methoxybenzophenone,2,2'-dihydroxy-4,4'-dimethoxybenzophenone,2,2'-dihydroxy-4-methoxybenzophenone,2-hydroxy-4-n-octyloxybenzophenone,2-hydroxy-4-n-dodecyloxybenzophenone,2-hydroxy-4-octadecyloxybenzophenone, 2,4-dihydroxybenzophenone,2-hydroxy-4-benzoyloxybenzophenone, 2,6-dihydroxy-5-benzoylbenzophenone,bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane,2,2',4,4'-tetrahydroxybenzophenone,2-hydroxy-4-methoxy-2'-carboxybenzophenone,2-hydroxy-4-methoxy-4'-chlorobenzophenone,2-hydroxy-5-chlorobenzophenone, and2-hydroxy-4-methoxybenzophenone-5-sulfonic acid; acetophenone compoundssuch as 2-hydroxy-5-methoxyacetophenone; benzotriazole compounds such as2-(2'-hydroxy-5'-methylphenyl)benzotriazole,2-(2'-hydroxy-3',5'-diisoamylphenyl)benzotriazole,2-[2'-hydroxy-3',5'-bis(α,α-dimethylbenzyl)phenyl]benzotriazole,2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole,2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole,2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole,2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole, and2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-(2-N-benzotriazole-2-yl)phenol],benzoate compounds such as phenyl salicylate, 4-t-butylphenylsalicylate, 4-t-octylphenyl salicylate, dibenzoylresorcinol,tribenzoylresorcinol, bis(4-t-butylbenzoyl)resorcin, ethylene glycolmonosalicylate, and 2,4-di-t-butylphenyl 3,5'-di-t-butyl-4'-hydroxybenzoate; oxalic anilide compounds such as2-ethoxy-2'-ethyloxalic acid bisanilide and2-ethoxy-5-t-butyl-2'-ethyloxalic acid bisanilide; cyanoacrylatecompounds such as 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, ethyl2-cyano-3,3-diphenylacrylate and n-butyl2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate; organic nickel compoundssuch as nickel bis(octylphenyl)sulfide, n-butylamine nickel[2,2'-thiobis(4-t-octyl phenolate)], 2-ethylhexylamine nickel[2,2'-thiobis(4-t-octyl phenolate)], nickel dibutyldithiocarbamate andtriethanolamine nickel [2,2'-thiobis(4-t-octylphenolate)]; and hinderedpiperazine compounds such astetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate,bis(N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate, condensationproduct of dimethyl succinate and2-(4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl)ethanol, phenyl4-piperidylcarboxylate, and 1,1'-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone).

It is also possible to choose and use, as needed, one or more of thefollowing additives: nucleating agents, for example, 4-t-butyl benzoate,adipic acid and diphenyl acetate; metal inactivating agents, forexample, oxanilide, dicarboxylic dihydrazides, dicarboxylicbisphenylhydrazides, salicylic hydrazide,N-salicyloyl-N'-salicylidenehydrazine, bis-salicyloydicarboxylicdihydrazides, bis-diacylated dicarboxylic dihydrazides,salicyloyl-hydrazinotriazine, bis-salicyloyl hydrazine and oxalicbis(benzilidenehydrazide); free radical promoters, for example,2,3-dimethyl-2,3-diphenylbutane ("INTALOX CC DFB", trade name; productof Peroxyd Chemie GmbH), 3,4-dimethyl-3,4-diphenylhexane ["INTALOX CCDFH", trade name; product of Peroxyd Chemie GmbH),2,3-dimethyl-2,3-diphenylhexane, cyclohexenecarboguanamine andnorbornanecarboquanamine.

In the flame-retarding method of the present invention, no particularlimitation is imposed on the manner of production of the resincomposition. It is possible to apply any production method which isgenerally employed upon mixing powdery additives in such a resin. In thecase of a thermoplastic resin or the like, for example, the resin in theform of pellets or a powder is mixed in advance with additives at roomtemperature and the resulting mass is melted, mixed and then formed byan extruder, a heating roll, a kneader or the like. As an alternative, aresin containing the additives at high concentrations is producedbeforehand and is then melted and kneaded together with the ordinaryresin, and the resulting mass is thereafter formed. In the case of athermosetting resin or the like, on the other hand, one or morecomponents essential to the present invention are added, before curing,to a monomer or prepolymer or to a dope or compound which has beenformed by adding one or more reinforcing materials to the monomer orprepolymer. The resulting mixture is then kneaded, formed and cured. Itis however to be noted that the practice of the present invention shallnot be limited to such production methods.

In the flame-retarding method of the present invention, one or moreother additives can also be incorporated as needed to extent notimpairing the advantageous effects of the present invention.Illustrative examples of such additives include plasticizers, dyes andpigments, dispersants, organic chelating agents, stabilizers, foamingagents, antihazing agents, delustering agents, surface treatments,fluorescent agents, mildewproofing agents, bacteriocides, antioxidants,ultraviolet light absorbers, conventional flame retardants orflame-retarding aids such as antimony trioxide, barium metaborate,zirconium dioxide, lead oxide and zinc borate, lubricants such as higherfatty acids, higher fatty acid esters, higher fatty acid metal salts andbisamides, antistatic agents such as sulfonic acids, quaternary ammoniumsalts, polyhydric alcohol esters, alkylamides, alkylamines andelectrically conductive carbon black, reinforcing materials such asglass fibers and carbon fibers; fillers such as talc, clay, calcinedclay, mica, calcium silicate, calcium sulfate, calcium carbonate, glassbeads, molybdenum disulfide and graphite, processing aids, partingagents, and other polymers.

In the flame-retarding method of the present invention, it is preferredto additionally incorporate at least one flame-retarding aid selectedfrom phosphoruses consisting of simple substances of phosphorus andphosphorus-containing compounds.

Preferred phosphoruses are, for example, red phosphorus, phosphoricacid, polyphosphoric acids, phosphorous acid, phosphonic acid, phosphatesalts, polyphosphate salts, phosphite salts, phosphonate salts,phosphate esters, phosphite esters, phosphonate esters, phosphines andsulfur-containing phosphorus compounds. Particularly preferredpolyphosphate salts are ammonium polyphosphates represented by thefollowing formula:

    (NH.sub.4).sub.n+2 P.sub.n O.sub.3n+1

wherein n stands for an integer greater than 5.

As an alternative, it is also preferred to additionally incorporate atleast one flame-retarding aid selected from the isocyanuric acids andcyanuric acids represented by formula (9) and formula (10),respectively.

As a further alternative, it is also preferred to additionallyincorporate at least one flame-retarding aid selected fromamino-containing compounds. Preferred are, for example, compoundscontaining at least one group selected from >N--CH₂ CH₂ --N<, ##STR20##dicyandiamide and guanidine, and their reaction products with aldehydesor epoxy compounds.

It is particularly preferred to incorporate the above-describedphosphoruses and amino-containing compounds together as flame-retardingaids.

The resin to which the flame-retarding method of this invention isapplied is preferably a thermoplastic resin. The thermoplastic resin canpreferably be at least one thermoplastic resin selected from the groupconsisting of polyolefin resins, polyamide resins, styrene resins,polyphenylene ether resins, saturated polyester resins, polycarbonateresins, polyacetal resins and acrylic resins.

As the resin, a thermosetting resin is also preferred. Thisthermosetting resin can preferably be at least one thermosetting resinselected from the group consisting of unsaturated polyester resins,diallyl phthalate resins, epoxy resins and urethane resins.

Thermal Stabilization Method

Owing to the incorporation of the diguanamine of formula (1) or (2) inthe resin, the thermal stabilization method according to the presentinvention can substantially improve the thermal stability, ultravioletlight resistance and the like of the resin and moreover can minimizecoloration or discoloration of the resin during its processing andformation at high temperatures. The diguanamine is excellent inhigh-temperature stability, non-volatility and handling and, moreover,can significantly protect the resin from decomposition or deteriorationby heavy metal ions such as copper ions.

In the thermal stabilization method of the present invention, thediguanamine is used in an amount of 0.01-5 wt. %, preferably 0.02-1 wt.% based on the resin. Amounts smaller than 0.01 wt. % can hardly exhibitsufficient effects for the improvement of stability to heat, light andthe like, whereas amounts greater than 5 wt. % cannot bring about anysubstantial extra advantage for the improvement of the stability and arenot preferred economically.

Resins to which the thermal stabilization method of this invention canbe applied are substantially the same as those described above as resinsto which the flame-retarding method of this invention is applicable. Thethermal stabilization method of this invention can enhance itsstability-improving effects still further when additives such as theabove-described phenolic antioxidants, amine-base antioxidants,sulfur-containing antioxidants, light stabilizers, nucleating agents andother additives are additionally used in amounts similar to thosespecified above or the below-described phosphite antioxidants are usedadditionally. These additives can be chosen as needed depending on theapplication purpose.

Incidentally, illustrative examples of phosphite antioxidants includetriphenyl phosphite, tris(nonylphenyl) phosphite, tris(dinonylphenyl)phosphite, tris(2,4-di-t-butylphenyl) phosphite,tris(2,5-di-t-butylphenyl) phosphite, tris(2,6-di-t-butylphenyl)phosphite, tris(mono/di-mixed nonylphenyl) phosphite, diphenyl decylphosphite, 2-ethylhexyl diphenyl phosphite, phenyl diisodecyl phosphite,diphenyl acid phosphite, trilauryl phosphite, tridecyl phosphite,tris(2-ethylhexyl) phosphite, tributyl phosphite, dibutyl acidphosphite, dilauryl acid phosphite, ditridecylpentaerythritoldiphosphite, distearyl pentaerythritoldiphosphite,bis(2,4-di-t-butylphenyl)pentaerythritoldiphosphite,bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritoldiphosphite,bis(nonylphenyl) pentaerythritoldiphosphite, diisodecylpentaerythritoldiphosphite, phenyl 4,4'-isopropylidenediphenolpentaerythritoldiphosphite, trilauryl trithiophosphite,tris(lauryl-2-thioethyl)phosphite, diphenylbis[4,4'-n-butylidenebis(2-t-butyl-5-methylphenol)]thiodiethanoldiphosphite,bis(neopentylglycol) 1,4-cyclohexanedimethylenephosphite, hydrogenated4,4'-isopropylidenediphenol polyphosphite, bis(octylphenyl)bis[4,4'-n-butylidenebis(2-t-butyl-5-methylphenol)]1,6-hexanedioldiphosphite,tetratridecyl-4,4'-n-butylidenebis(2-t-butyl-5-methylphenol)diphosphite,tetratridecyl-1,1,3-tris(2'-methyl-5'-t-butyl-4'-oxyphenyl)butanediphosphite, and tetra(C₁₂₋₁₅ mixed alkyl) 4,4'-isopropylidenediphenyldiphosphite. Preferably these phosphite antioxidants can each be used inan amount of 0.01-1.0 wt. % based on the resin.

In the thermal stabilization method according to the present invention,production of each resin composition and use of other additives can beconducted in a similar manner to the above-described flame-retardingmethod but are not limited to the corresponding procedures in theflame-retarding method.

The resin to which the thermal stabilization method of this invention isapplied is preferably a thermoplastic resin. The thermoplastic resin canpreferably be at least one thermoplastic resin selected from the groupconsisting of polyphenylene ether resins, polyacetal resins, polyamideresins and polyolefin resins. More preferably, the polyolefine resin canbe at least one resin selected from the group consisting of polyethyleneresin, polypropylene resin and ethylene-propylene copolymers.

Compatibilizing Method

According to the compatibilizing method of this invention, thediguanamine represented by formula (1) or (2) is incorporated in a blendof at least two different kinds of resins which includes at least oneresin selected from polyamide resins, polyphenylene ether resins,polyimide resins and polyalamide resins. As a result, the compatibilityof the two or more resins of different kinds is substantially improvedand, moreover, coloration or discoloration of the resin is minimizedduring its processing and forming at high temperatures. The diguanamineis superb because it has excellent high-temperature stability andnon-volatility, undergoes minimized sublimation, bleeding or the like,facilitates the production of the resin composition, has good meltdispersibility in the polyamide resins, polyphenylene ether resins andthe like, and can improve the thermal stability of the resin. Thediguanamine can therefore provide an excellent modification method forresins.

In the compatibilizing method of this invention, the diguanamine can beused generally in an amount of 0.5-20 wt. %, based on the total amountof the resins.

The amount of diguanamine can be suitably chosen within the above rangeas needed. Amounts smaller than 0.5 wt. % can hardly bring aboutsufficient effects for the improvement of the compatibility, whereasamounts greater than 20 wt. % cannot bring about any substantial extraimproving effects but causes reductions in resin properties and are notpreferred either from the economical standpoint.

Resins to which the compatibilizing method of this invention can beapplied are substantially the same as those described above inconnection with the flame-retarding method. Specific examples of atleast two resins of different kinds include, but are not limited to,combinations of one type of resins selected from polyamide resins,polyphenylene ether resins, polyimide resins and polyaramid resins andresins other than the one type of resins, for example, polyamide resinsand ABS resins, polyamide resins and polyphenylene ether resins,polyimide resins and polyphenylene ether resins, as two resins ofdifferent kinds as well as polyamide resins, polyphenylene ether resinsand other resins as three or more different kinds.

In the compatibilizing method of the present invention, additives suchas the above-described phenolic antioxidants, amine-base antioxidants,sulfur-containing antioxidants, phosphite antioxidants, lightstabilizers, nucleating agents and other additives can be usedadditionally in amounts similar to those described above. Theseadditives can be chosen as needed depending on the application purpose.

Further, production of a resin composition in accordance with thecompatibilizing method of this invention can be conducted in a similarmanner to the production according to the above-describedflame-retarding method, although the former production is not limited tothe latter one.

Diguanamine Derivatives

In addition of the use of the diguanamines represented by formula (1) or(2), the present invention also provides derivatives of thesediguanamines, their preparation process and their use.

Examples of such diguanamine derivatives include diguanamine derivativesrepresented by the following formula (11): ##STR21## wherein the bondingsites of the 1,3,5-triazin-2-yl groups are the 2,5- or 2,6-positions,and Y₁, Y₂, Y₃, Y₄, Y₅, Y₆, Y₇ and Y₈ are the same or different andindividually represent a substituent selected from the group consistingof a hydrogen atom and groups containing at least two carbon atoms, withthe proviso that at least one of Y₁, Y₂, Y₃, Y₄, Y₅, Y₆, Y₇ and Y8 is agroup containing at least two carbon atoms, and those represented by thefollowing formula (12): ##STR22## wherein the bonding sites of the1,3,5-triazin-2-yl groups are the 1,2-, 1,3- or 1,4-positions and Y₁,Y₂, Y₃, Y₄, Y₅, Y₆, Y₇ and Y₈ have the same meanings as defined informula (11).

In the diguanamine derivatives [formula (11)] according to thisinvention, the bonding sites of the 1,3,5-triazin-2-yl groups are the2,5- or 2,6-positions. The configuration of such groups is an endo--endoform, endo-exo form or exo--exo form. These stereoisomers are all usefulderivatives. In the diguanamine derivatives [formula (12)], the bondingsites of the 1,3,5-triazin-2-yl groups are the 1,2-, 1,3- or 1,4positions. The configuration of such groups is a trans or cis form.These stereoisomers are all useful derivatives. Although suchdiguanamine derivatives are derivatives selected from the groupconsisting of the above-described isomers in bonding sites orconfiguration, mixtures of different derivatives and/or isomers selectedfrom such a group are also extremely useful from the industrialviewpoint like the individual derivatives.

In formulas (11) and (12), at least one of Y₁, Y₂, Y₃, Y₄, Y₅, Y₆, Y₇and Y₈ is a group containing at least two carbon atoms. No particularlimitation is imposed in number, position, configuration and the like onthe group containing at least two carbon atoms. Diguanamine derivativesin which each of Y₂, Y₄, Y₆ and Y₈ is a hydrogen atom, and Y₁, Y₃, Y₅and Y₇ are individually a hydrogen atom or a group containing at leasttwo carbon atoms, for example, N-mono-substituted diguanaminederivatives, N,N'-di-substituted diguanamine derivativesN,N',N"-tri-substituted diguanamine derivatives,N,N',N",N"'-tetra-substituted diguanamine derivatives and the like arepreferred from the viewpoints of preparation and applications, that is,for the availability of raw materials, the readiness of reactions, thesimpleness and convenience of steps such as purification and isolation,and the possibility of easy preparation from amines containing one aminogroup. Particularly preferred are N,N',N"-tri-substituted diguanaminederivatives and N,N',N",N" '-tetra-substituted diguanamine derivatives.

Y₁, Y₂, Y₃, Y₄, Y₅, Y₆, Y₇ and Y₈ in formulas (11) and (12) individuallyrepresent a substituent selected from the group consisting of a hydrogenatom and groups containing two or more carbon atoms. Useful examples ofthe groups containing two or more carbon atoms include aliphatic,alicyclic, aromatic and heterocyclic groups, which may optionallycontain one or more branch chains, functional groups such as hydroxy,ester, ether, carboxyl, carbonyl, amido, imido, nitro, sulfonic,sulfonamido, amino, imino and/or unsaturated groups and the like.Illustrative of such groups include, but are not limited to, aliphaticgroups, alicyclic groups, aromatic groups, heterocyclic groupscontaining 2-30 carbon atoms, groups represented by HO--Y₉ -- in whichY₉ is a divalent group containing at least 2 carbon atoms, groupsrepresented by the following formula (13): ##STR23## wherein Y₁₀ is agroup selected from the group consisting of ethylene, trimethylene andtetramethylene which may optionally contain one or more substituentgroups containing 2-22 carbon atoms, m is an integer selected from 1 to100, and Y₉ has the same meaning as defined above, and groupsrepresented by the following formula (14): ##STR24## wherein Y₁₀ and mhave the same meanings as defined in formula (13).

Specific examples of such aliphatic groups alicyclic groups andheterocyclic groups containing 2-30 carbon atoms include, but are notlimited to, ethyl, isopropyl, isobutyl, n-butyl, 1,2-dimethylpropyl,n-hexyl, n-octyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl,octadecyl, allyl, oleyl, 4-aminobutyl, 3-ethoxypropyl, butoxypropyl,myristyloxypropyl, methoxyethyl, ethoxyethyl, cyclohexyl,4-methylcyclohexyl, phenyl, o-tolyl, e-naphthyl, benzyl, β-phenethyl,o-methoxycarbonylphenyl, p-ethoxycarbonylphenyl, 4-methoxyphenyl,tetrahydrofurfuryl, 2-(1-piperazinyl)ethyl, 2-piperidinoethyl,2-morpholinoethyl, 3-morpholinopropyl, 2-(1-pyrrolidinyl)ethyl, and2-pyridinyl.

In the groups represented by HO--Y₉ --, Y₉ is a divalent groupcontaining at least two carbon atoms, for example, a aliphatic,alicyclic, aromatic or heterocyclic group. Although no other particularlimitation is imposed on Y₉, those containing 2-20 carbon atoms arepreferred from the standpoint of production such as the availability ofraw materials, the readiness of a reaction, and the simpleness andconvenience of purification, isolation and like steps and also from thestandpoint of application. As such groups contain a hydroxyl group, thecorresponding diguanamine derivatives are extremely useful for a widevariety of applications such as resin raw materials, modifiers andcrosslinking agents.

Specific examples of the group represented by HO--Y₉ -- include, but arenot limited to, 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl,1-hydroxymethylpropyl, 3-hydroxypropyl, 2-hydroxy-2-methylpropyl,5-hydroxypentyl, 1-(2-hydroxyethyl)propyl, 3-hydroxypentyl,3-hydroxy-2,2-dimethylpropyl, 1-hydroxyhexyl, 1-ethyl-3-hydroxybutyl,8-hydroxyoctyl, 10-hydroxydecyl, 12-hydroxydodecyl,1-(2-hydroxyethyl)-2-propenyl, 1-(3-hydroxypropyl)-1-propenyl,1-(2-hydroxypropyl)-2-propenyl, 1-(1-hydroxypropyl)-3-pentenyl,5-hydroxy-3-oxapentyl, 1-hydroxymethyl-3-oxabutyl,1-(2-hydroxyethyl)-4-oxahexyl, 1-(2-hydroxypropyl)-5-oxahexyl,4-hydroxycyclohexyl, 4-hydroxyphenyl, 2-methyl-4-hydroxyphenyl,7-hydroxynaphthyl, 4-(hydroxymethyl)phenyl, 2-(4-hydroxyphenyl)ethyl,4-(2-hydroxyethyl)phenyl, 3-hydroxypyridin-2-yl, and8-hydroxyquinolin-4-yl.

In the group represented by formula (13), Y₉ represents is a divalentgroup containing at least two carbon atoms, for example, a divalentaliphatic, alicyclic, aromatic or heterocyclic group having at least twocarbon atoms. Although no other particular limitation is imposedthereon, those containing 2-20 carbon atoms are preferred. Specificexamples of Y₉ include, but are not limited to, residual groups whichare formed by removing the hydroxyl group from the groups mentionedabove as specific examples of the group represented by HO--Y₉ --.

Y₁₀ in the groups represented by formulas (13) and (14), respectively,represents a group selected from the group consisting of ethylene,trimethylene and tetramethylene, which may optionally contain one ormore substituent groups containing 2-22 carbon atoms. Useful examples ofthe groups include, but are not particularly limited to, aliphatic,alicyclic, aromatic and heterocyclic groups which may optionally containone or more of various functional groups and/or branch chains. No otherparticular limitation is imposed on Y₁₀. Specific examples of Y₁₀include, but are not limited to, ethylene, propylene, ethylethylene,n-butylethylene, n-dodecylethylene, phenylethylene, butoxyethylene,phenoxyethylene, 3-acryloxylpropylene, 1,2-cyclohexylene,tricyclo[4.3.1.0]-deca-7-ene-2,3-diyl, trimethylene and tetramethylene,with ethylene and propylene being preferred. In the groups representedby formula (13) and (14), respectively, in which n is other than 1,plural Y₁₀ s may be the same or different. Where such plural Y₁₀ s aredifferent, they can be arranged at random or in block(s). The kind andarrangement of such plural Y₁₀ s can be chosen freely as needed.

Further, m is an integer selected from 1-100 and cam be chosen freely asneeded. However, it is generally an integer in a range of 1-50,preferably an integer in a range of 1-30.

The above-described oxaalkyl-containing diguanamine derivative is aderivative containing 1-8 groups selected from the groups represented byformula (13) or formula (14). One or more kinds of such groups may becontained in the same derivative. For the readiness of reactions, theavailability of raw materials and the like, particularly usefuloxaalkyl-containing diguanamine derivatives represented by formula (13)include, but are not limited to, N-mono-substituted oxaalkylateddiguanamine derivatives, N,N'-di-substituted oxaalkylated diguanaminederivatives, N,N',N"-tri-substituted oxaalkylated diguanaminederivatives and N,N',N",N"'-tetra-substituted oxaalkylated diguanaminederivatives, in which the substituents are such groups as describedabove. For the availability of raw materials, particularly usefulexamples of the oxaalkyl-containing diguanamine derivative representedby formula (14) include, but are not limited to, oxaalkyl-containingdiguanamine derivatives containing 3-8 groups selected from thosedescribed above.

Specific examples of the diguanamine derivative according to the presentinvention include, but are not limited to,2-(4,6-diamino-1,3,5-triazin-2-yl)-5-(4-amino-6-n-octylamino-1,3,5-triazin-2-yl)-bicyclo-[2.2.1.]heptane,2-(4,6-diamino-1,3,5-triazin-2-yl)-6-(4-amino-6-anilino-1,3,5-triazin-2-yl)-bicyclo[2.2.1]-heptane,2-(4,6-diamino-1,3,5-triazin-2-yl)-5-[4-amino-6-(2-morpholinoethylamino)-1,3,5-triazin-2-yl]-bicyclo-[2.2.1]heptane,1-(4,6-diamino-1,3,5-triazin-2-yl)-2-(4-amino-6-cyclohexylamino-1,3,5-triazin-2-yl)-cyclohexane,1-(4,6-diamino-1,3,5-triazin-2-yl)-4-[4-amino-6-(2-morpholinoethylamino)-1,3,5-triazin-2-yl]cyclohexane,2-(4,6-diamino-1,3,5-triazin-2-yl)-5-[4-amino-6-(2-hydroxyethylamino)-1,3,5-triazin-2-yl]-bicyclo-[2.2.1]heptane,2-(4,6-diamino-1,3,5-triazin-2-yl)-6-[4-amino-6-(2-hydroxypropylamino)-1,3,5-triazin-2-yl]-bicyclo[2.1]heptane,2-(4,6-diamino-1,3,5-triazin-2-yl)-6-[4-amino-6-(5-hydroxy-3-oxapentylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,2-(4,6-diamino-1,3,5-triazin-2-yl)-5-[4-amino-6-(4-hydroxyphenylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,1-(4,6-diamino-1,3,5-triazin-2-yl)-3-[4-amino-6-(2-hydroxyethylamino)-1,3,5-triazin-2-yl]-cyclohexane,1-(4,6-diamino-1,3,5-triazin-2-yl)-4-[4-amino-6-(3-hydroxypropylamino)-1,3,5-triazin-2-yl]-cyclohexane,1-(4,6-diamino-1,3,5-triazin-2-yl)-3-[4-amino-6-(5-hydroxy-3-oxapentylamino)-1,3,5-triazin-2-yl]-cyclohexane,1-(4,6-diamino-1,3,5-triazin-2-yl)-4-[4-amino-6-(4-hydroxyphenylamino)-1,3,5-triazin-2-yl]-cyclohexane,2,5-bis(4-amino-6-cyclohexylamino-1,3,5-triazin-2-yl)-bicyclo[2.2.1]heptane,2,6-bis(4-amino-6-benzylamino-1,3,5-triazin-2-yl)-bicyclo[2.2.1]heptane,2,5-bis(4-amino-6-(2-morpholinoethylamino)-1,3,5-triazin-2-yl)-bicyclo[2.2.1]heptane,2-(4,6-diamino-1,3,5-triazin-2-yl)-6-[4,6-bis(4-methoxycarbonylphenylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,1,4-bis(4-amino-6-n-decylamino-1,3,5-triazin-2-yl)-cyclohexane,1,3-bis[4-amino-6-(2-morpholinoethylamino)-1,3,5-triazin-2-yl)-cyclohexane,1-(4,6-diamino-1,3,5-triazin-2-yl)-2-(4,6-dianilino-1,3,5-triazin-2-yl)-cyclohexane,2,5-bis[4-amino-6-(2-hydroxyethylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,2,6-bis[4-amino-6-(2-hydroxypropylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,2,5-bis[4-amino-6-(5-hydroxy-3-oxapentylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]-heptane,2,5-bis[4-amino-6-(4-hydroxyphenylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,2-(4,6-diamino-1,3,5-triazin-2-yl)-6-[4,6-bis(2-hydroxyethylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,1,4-bis[4-amino-6-(2-hydroxyethylamino)-1,3,5-triazin-2-yl)-cyclohexane,1,3-bis[4-amino-6-(3-hydroxypropylamino)-1,3,5-triazin-2-yl]-cyclohexane,1-(4,6-diamino-1,3,5-triazin-2-yl)-4-[4,6-bis(5-hydroxy-3-oxapentylamino)-1,3,5-triazin-2-yl]-cyclohexane,2-(4-amino-6-cyclohexylamino-1,3,5-triazin-2-yl)-5-[4,6-bis(cyclohexylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,2-[4-amino-6-(2-morpholinoethylamino)-1,3,5-triazin-2-yl]-6-[4,6-bis(2-morpholinoethylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,1-[4-amino-6-(4-ethoxycarbonylphenylamino)-1,3,5-triazin-2-yl]-4-[4,6-bis(4-ethoxycarbonylphenylamino)-1,3,5-triazin-2-yl]-cyclohexane,2-[4-amino-6-(2-hydroxyethylamino)-1,3,5-triazin-2-yl]-6-[4,6-bis(2-hydroxyethylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,2-[4-amino-6-(2-hydroxypropylamino)-1,3,5-triazin-2-yl]-5-[4,6-bis(2-hydroxypropylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]-heptane,2-[4-amino-6-(2-hydroxyethylamino)-1,3,5-triazin-2-yl]-5-[4,6-bis(5-hydroxy-3-oxapentyl)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,2-[4-amino-6-(5-hydroxy-3-oxapentylamino)-1,3,5-triazin-2-yl]-6-[4,6-bis(5-hydroxy-3-oxapentylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,2-[4-amino-6-(4-hydroxyphenylamino)-1,3,5-triazin-2-yl]-5-[4,6-bis(4-hydroxyphenylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,2-[4-amino-6-anilino-1,3,5-triazin-2-yl]-6-[4,6-bis(3-hydroxypropylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]-heptane,1-[4-amino-6-(2-hydroxyethylamino)-1,3,5-triazin-2-yl]-4-[4,6-bis(2-hydroxyethylamino)-1,3,5-triazin-2-yl]-cyclohexane,1-[4-amino-6-(1-hydroxymethylpropylamino)-1,3,5-triazin-2-yl]-3-[4,6-bis(1-hydroxymethylpropylamino)-1,3,5-triazin-2-yl]-cyclohexane,1-[4-amino-6-(5-hydroxy-3-oxapentylamino)-1,3,5-triazin-2-yl]-4-[4,6-bis(5-hydroxy-3-oxapentylamino)-1,3,5-triazin-2-yl]-cyclohexane,1-[4-amino-6-(4-amino-6-(4-hydroxyphenylamino)-1,3,5-triazin-2-yl]-2-[4,6-bis(4-hydroxyphenylamino)-1,3,5-triazin-2-yl]-cyclohexane,2,5-bis[4,6-bis(n-octylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,2,6-bis[4,6-bis-(cyclohexylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]-heptane,2,5-bis[ 4,6-dianilino-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,2,5-bis[4,6-bis(2-morpholinoethylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,2,6-bis[4,6-bis(3-oxapentylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,2,5-bis[4,6-bis(4-methoxycarbonylphenylamino)-1,3,5-triazin-2-yl]-bicyclo-[2.2.1]heptane,1,3-bis[4,6-bis(cyclohexylamino)-1,3,5-triazin-2-yl]-cyclohexane,1,4-bis[4,6-bis(2-morpholinoethylamino)-1,3,5-triazin-2-yl]-cyclohexane,1,2-bis[4,6-bis(3-oxapentylamino)-1,3,5-triazin-2-yl]-cyclohexane,1,4-bis[4,6-bis(4-ethoxycarbonylphenylamino)-1,3,5-triazin-2-yl]-cyclohexane,2,5-bis[4,6-bis(2-hydroxyethylamino)-1,3,5-triazin-2-yl]-bicyclo-[2.2.1]heptane,2,6-bis[4,6-bis(2-hydroxypropylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,2,6-bis[4,6-bis(1-hydroxymethylpropylamino)-1,3,5-triazin-2-yl]bicyclo-[2.2.1]heptane,2,5-bis[4,6-bis(3-hydroxypropylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,2,5-bis[4,6-bis(5-hydroxy-3-oxapentylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,2,6-bis[4,6-bis(5-hydroxy-3-oxapentylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]-heptane,2,6-bis[4,6-bis(4-hydroxyphenylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,2,5-bis[4,6-bis(N,N-di-n-butylamino)-1,3,5-triazin-2-yl]-bicyclo-[2.2.1]heptane,1,3-bis[4,6-bis(2-hydroxyethylamino)-1,3,5-triazin-2-yl]-cyclohexane,1,4-bis[4,6-bis(2-hydroxypropylamino)-1,3,5-triazin-2-yl]-cyclohexane,1,2-bis[4,6-bis(1-hydroxymethylpropylamino)-1,3,5-triazin-2-yl]-cyclohexane,1,4-bis[4,6-bis(3-hydroxypropylamino)-1,3,5-triazin-2-yl]-cyclohexane,1,3-bis[4,6-bis(5-hydroxy-3-oxapentylamino)-1,3,5-triazin-2-yl]-cyclohexane,1,4-bis[4,6-bis(4-hydroxyphenylamino)-1,3,5-triazin-2-yl]-cyclohexane,polyoxyethylenated2,5-bis[4,6-diamino-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,polyoxypropylenated2,6-bis[4,6-diamino-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,polyoxyethylenated2-[4,6-diamino-1,3,5-triazin-2-yl]-6-[4-amino-6-anilino-1,3,5-triazin-2-yl]-bicyclo-[2.2.1]heptane,polyoxyethylenated2,6-bis[4-amino-6-(2-hydroxypropylamino)-1,3,5-triazin-2-yl]-bicyclo-[2.2.1]heptane,polyoxypropylenated2-[4-amino-6-(2-hydroxyethylamino)-1,3,5-triazin-2-yl]-5-[4,6-bis(2-hydroxyethylamino)-1,3,5-triazin-2-yl-bicyclo[2.2.1]-heptane,polyoxyethylenated2,6-bis[4,6-bis(5-hydroxy-3-oxapentylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]-heptane,polyoxyethylenated2,5-bis[4,6-bis(2-hydroxypropylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,polyoxypropylenated2,6-bis[4,6-bis(4-hydroxyphenylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,polyoxyethylenated2,5-bis[4,6-bis(N,N-dimethylolamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,polyoxypropylenated2,6-bis[4,6-bis(N-methylolamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,polyoxyethylenated 1,4-bis(4,6-diamino-1,3,5-triazin-2-yl)-cyclohexane,polyoxypropylenated 1,3-bis(4,6-diamino-1,3,5-triazin-2-yl)-cyclohexane,polyoxystyrenated1-[4,6-diamino-1,3,5-triazin-2-yl)-2-(4-amino-6-benzylamino-1,3,5-triazin-2-yl)-cyclohexane,polyoxypropylenated1,4-bis[4,6-bis(2-hydroxypropylamino)-1,3,5-triazin-2-yl)-cyclohexane,polyoxyethylenated1,3-bis[4,6-bis(4-hyroxyphenylamino)-1,3,5-triazin-2-yl]-cyclohexane,polyoxyethylenated1,4-bis[4,6-bis-(N,N-dimethylolamino)-1,3,5-triazin-2-yl]-cyclohexane,polyoxypropylenated1,3-bis[4,6-bis(N-methylolamino)-1,3,5-triazin-2-yl)-cyclohexane,2-(4,6-diamino-1,3,5-triazin-2-yl)-5-[4-amino-6-(2-piperazinoethylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,2,6-bis[4,6-bis(2-aminoethylamino)-1,3,5-triazin-2-yl]-bicyclo-[2.2.1]heptane,2,5-bis[4,6-bis(2-piperidinoethylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,2,6-bis[4,6-bis(3-piperazinopropylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane,2,5-bis[4,6-bis(N-aminoethylpiperazinoethylamino)-1,3,5-triazin-2-yl]-bicyclo-[2.2.1]heptane,1,3-bis[4,6-bis(2-piperazinoethylamino)-1,3,5-triazin-2-yl]-cyclohexane,and1,4-bis-[4,6-bis{3-piperidinopropylamino)-1,3,5-triazin-2-yl]-cyclohexane.

Among the above-described diguanamine derivatives according to thepresent invention, preferred are hydroxyl-containing diguanaminederivatives in which Y₁, Y₂, Y₃, Y₄, Y₅, Y₆, Y₇ and Y₈ in formula (11)or (12) individually represent a substituent selected from the groupconsisting of a hydrogen atom and groups represented by HO--Y₉ --, Y₉being a divalent group containing at least two carbon atoms.

Also preferred are hydroxyl-containing diguanamine derivatives in whichHO--Y₉ -- is a group selected from the group consisting of2-hydroxyethyl, 2-hydroxypropyl, 1-hydroxymethylpropyl, 3-hydroxypropyl,5-hydroxy-3-oxapentyl and 4-hydroxyphenyl groups.

Also preferred are oxaalkyl-containing diguanamine derivativesrepresented by formula (11) or (12) in which at least one of Y₁, Y₂, Y₃,Y₄, Y₅, Y₆, Y₇ and Y₈ represents a group selected from the groupconsisting of groups represented by formula (13) or (14). Morepreferably, Y₁₀ in formula (13) or (14) is at last one group selectedfrom ethylene and propylene.

Each diguanamine derivative represented by formula (11) or (12) can beprepared by reacting at least one diguanamine, which is selected fromthe diguanamines represented by formula (1) or (2), with at least oneamine selected from amines containing one or more amino groups and atleast two carbon atoms.

As the amine for the above-described preparation of the diguanaminederivative, any amine can be used insofar as it contains at least oneamino group and two or more carbon atoms. No particular limitation isimposed on the number of amino group(s). The amine contains analiphatic, alicyclic, aromatic or heterocyclic group having two or morecarbon atoms. Although no other particular limitation is imposed on theamines, those containing 2-20 carbon atoms are preferred for theavailability of raw materials, the readiness of reactions, and thesimpleness and convenience of steps such as purification and isolation,The amine may contain one or more groups other than amino group(s), forexample, hydroxyl, ester, ether, carboxyl, carbonyl, amido, imido,sulfonic, carboxamido, imino and/or unsaturated groups. Those containingone or more hydroxyl, ester, ether and/or imino groups are particularlyuseful.

Specific examples of such amines include, but are not limited to,compounds represented by HO--Y₉ --NH₂ in which Y₉ represents a divalentgroup containing at least two carbon atoms, such as 2-aminoethanol,3-amino-1-propanol, 2-amino-1-propanol, 1-amino-2-propanol,4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-methyl-2-propanol,5-amino-1-pentanol, 3-amino-1-pentanol, 1-amino-3-pentanol,2,2-dimethyl-3-amino-1-propanol, 6-amino-1-hexanol, 4-amino-2-hexanol,8-amino-1-octanol, 10-amino-1-decanol, 12-amino-1-dodecanol,3-amino-1-penten-5-ol, 4-amino-2-hexen-6-ol, 3-amino-1-hexen-5-ol,5-amino-2-octen-6-ol, 5-amino-3-oxapentan-1-ol,2-amino-3-methoxy-1-propanol, 3-amino-5-ethoxy-1-pentanol,4-amino-7-methoxy-2-heptanol, 4-amino-1-cyclohexanol, p-aminophenol,4-amino-m-cresol, p-aminophenyl ethanol, 8-amino-2-naphthol,p-aminobenzyl alcohol, 4-hydroxyphenethylamine,2-amino-3-hydroxypyridine and 5-amino-8-hydroxyquinoline; aliphaticmonoamines such as ethylamine, isopropylamine, butylamine,1,2-dimethylpropylamine, hexylamine, 2-ethylhexylamine, dodecylamine,tetradecylamine, hexadecylamine, octadecylamine, allylamine, oleylamine,3-ethoxypropylamine, propoxypropylamine, butoxypropylamine,2-ethylhexyloxypropylamine and myristyloxypropylamine; aromaticmonoamines such as aniline, o-toluidine, α-naphthylamine,β-phenethylamine and benzylamine; alicyclic monoamines such ascyclohexylamine and 4-methylcyclohexylamine; heterocyclic monoaminessuch as furfurylamine, N-(2-aminoethyl)morpholine,N-(2-aminoethyl)piperidine, N-(3-aminopropyl)piperazine and2-aminopyridine; polyamines such as 1,2-ethylenediamine,1,3-diaminopropane, 1,2-diaminopropane, 1,4-butylenediamine,1,6-hexamethylenediamine, 1,4-diaminocyclohexane,1,3-bis(aminomethyl)cyclohexane, N-(2-aminoethyl)piperazine,N,N'-bis(2-aminoethyl)piperazine, m-phenylenediamine, benzidine,4,4'-diaminodiphenylmethane, xylylenediamine and1,2-bis(3-aminopropoxy)ethane; alkyl aminobenzoates such as ethylp-aminobenzoate, methyl anthranylate and butyl m-aminobenzoate; andpolyalkylenepolyamines such as diethylenetriamine, triethylenetetramine,tetraethylenepentamine and pentaethylenehexamine. The compoundsrepresented by HO--Y₉ --NH₂ are particularly preferred as they canprovide hydroxyl-containing diguanamine derivatives useful for a widevariety of applications. The proportion of an amine to be used can bechosen freely as needed. It is generally used in a proportion of 0.5-20moles, preferably 1-16 moles per mole of the diguanamine. When an aminewhich tends to form byproducts such as cyclized compounds, such as1-aminoethanol, is used, it is preferred to conduct the reaction byusing the amine in a proportion of 8 moles or greater per mole of thecorresponding diguanamine to reduce byproduction. Use of the amine in anunduly large excess tends to develop a reduction in reaction velocity.In such a case, it is therefore preferred to choose and take a suitablemeasure, for example, to conduct the reaction by adding the amine eithercontinuously or discontinuously into the reaction system.

The above reaction can generally conducted at 120°-250° C., preferably150°-200° C. in the presence of an acidic catalyst.

Useful as the acidic catalyst is a compound or the like, which releasesor forms protons under reaction conditions. Illustrative acidiccatalysts include, but are not limited to, mineral acids such ashydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acidand phosphoric acid; sulfonic acids such as amidosulfonic acid,thiocyanic acid, p-toluenesulfonic acid and methanesulfonic acid;carboxylic acids such as trifluroacetic acid and trichloroacetic acid;salts of such acids with diguanamines, amines, ammonia or the like; andLewis acids such as boron trifluoride, aluminum chloride, tin (IV)chloride, antimony (V) fluoride and iron (III) bromide. The proportionof the acidic catalyst to be used can be chosen freely as needed.However the acidic catalyst is generally used at a ratio of 0.05-5.0moles, preferably 0.1-2.0 moles per mole of the correspondingdiguanamine.

The above reaction can be conducted in the presence or absence of asolvent. It is preferred to carry out the reaction in the absence of anysolvent. In some instances, however, a solvent can be chosen as needed,for example, from 1-pentanol, 2-methyl-1-butanol, 1-hexanol, 3-heptanol,1-octanol, 2-ethyl-1-hexanol, 1-decanol, ethylene glycol, 1,2-propyleneglycol, diethylene glycol, triethylene glycol, 2-methyl-2,4-pentanediol,ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethyleneglycol monobutyl ether, diethylene glycol dimethyl ether, diethyleneglycol dibutyl ether, diethylene glycol monomethyl ether, diethyleneglycol monoethyl ether, diethylene glycol monobutyl ether, triethyleneglycol dimethyl ether and triethylene glycol monoethyl ether.

No particular limitation is imposed on a system for the above reaction.It is however preferred to conduct the reaction in the presence of a gasinert to the reaction such as nitrogen or argon because the inert gas iseffective, for example, in reducing coloration of the reaction product.The reaction can be conducted under normal pressure or undernaturally-occurring pressure or elevated pressure within a closedvessel. These reaction conditions can be chosen freely as needed.

The hydroxyl-containing or oxaalkyl-containing diguanamine derivativesaccording to the present invention can each be prepared by subjecting atleast one diguanamine or diguanamine derivative--which is selected fromthe group consisting of the diguanamine derivatives containing an activehydrogen atom and represented by formula (11) or (12), diguanaminesrepresented by formula (1) or (2) and N-methylol derivatives ofdiguanamine--and at least one epoxide to an addition reaction.

The above process is excellent because it can easily provide in a highyield the hydroxyl-containing diguanamine derivatives and theoxaalkyl-containing diguanamine derivatives, the latter derivativescontaining at least one group selected from the group consisting ofgroups represented by formula (13) or (14).

As such diguanamine derivatives, those having anactive-hydrogen-containing group such as an imino, amino or hydroxylgroup are all useful. Useful examples of such diguanamine derivativesinclude, but are not limited to, diguanamine derivatives andhydroxyl-containing diguanamine derivatives, which are obtained byreacting diguanamine represented above formula (1) or (2) withamino-containing compounds having two or more carbon atoms such asaliphatic monoamines, alicyclic monoamines, aromatic monoamines,polyamines, compounds represented by HO--Y₉ --NH₂, Y₉ being a divalentgroup containing at least two carbon atoms, and the like, withhydroxyl-containing diguanamine derivatives being preferred. Suchdiguanamine derivatives are particularly preferred, as they haveexcellent features that their reactions can be carried out substantiallyin the absence of any solvent, they can be obtained in a high yield asgood reaction products having a narrow molecular weight distribution andhigh purity, and their preparation steps such as purification andisolation are simple.

As diguanamines, the compounds represented above by formula (1) or (2)are all useful. These compounds have excellent features absolutelyunpredictable from the known technology, that is, advantageous featuressuch that they have far better solubility in solvents compared withmelamines, their reactions can be carried out smoothly under milderconditions, and good products can be obtained with a desired molecularweight and a narrow molecular weight distribution than those availablefrom the melamine. These diguanamines are therefore extremely useful asraw materials for the preparation of the derivatives described above.

As N-methylol derivatives of diguanamines, those containing anN-methylol group and derived from the above-described diguanamines areall useful. Illustrative N-methylol derivatives of diguanamines include,but are not limited to, N-methyloldiguanamines obtained by subjectingthe above-described diguanamines and aldehydes such as formaldehyde toaddition reactions, respectively, etherified diguanamines by subjectingsuch N-methyloldiguanamines and alcohols having 1-20 carbon atoms toetherification, and primary condensates of N-methyloldiguanamine andprimary condensates of etherified diguanamine obtained by subjectingsuch N-methyloldiguanamines and etherified diguanamines to condensation,respectively. Preferred are N-methyloldiguanamines and primarycondensates of N-methyloldiguanamine, with N-methyloldiguanamines beingparticularly preferred. Such N-methylol derivatives of diguanamines haveadvantageous features extremely difficult to obtain with melamines andare preferred, as they are excellent inter alia in that their reactionscan be conducted substantially in the absence of any solvent, they canbe obtained as good products having a narrow molecular weightdistribution, their preparation steps such as purification and isolationare simple, polyols having eight hydroxyl groups can be easily obtained,and their yields are good.

As epoxides usable for the preparation of the diguanamine derivativesdescribed above, alkylene oxides containing one or more aliphatic groupsalicyclic groups, aromatic groups having 2-22 carbon atoms and/or thelike are useful. Illustrative of such epoxides include, but are notlimited to, ethylene oxide, propylene oxide, butylene oxide, isopreneoxide, n-hexene oxide, cyclohexene oxide, styrene oxide, cyclopentadienemonoxide, allyl glycidyl ether, n-butyl glycidyl ether, phenyl glycidylether, glycidyl methacrylate and butadiene oxide, with ethylene oxideand propylene oxide being preferred. These epoxides can be used eithersingly or in combination as mixtures. It is also possible to use them insuch a way that one of such epoxides is reacted, followed by reaction ofanother one. No particular limitations are imposed on the selection ofthese epoxides and the manner of the reaction such as the chargingmethod and sequence. The proportion of the epoxide can be chosen freelyas needed. However, the epoxide can be used generally in an amount of1-200 moles, preferably 2-100 moles, more preferably 4-20 moles per moleof the total amount of the diguanamine derivative, diguanamine and/orN-methyloldiguanamine derivative.

The above reaction is generally conducted at 80°-200° C., preferably100°-150° C. in the presence of a basic catalyst.

Examples of the basic catalyst include, but are not limited to, alkalimetal hydroxide and alkaline earth metal hydroxides such as lithiumhydroxide, potassium hydroxide, sodium hydroxide and calcium hydroxide;and alkali metal alcoholates such as sodium methylate, sodium ethylateand potassium ethylate. The proportion of the basic catalyst to be usedcan be chosen freely as needed. However, the basic catalyst can be usedgenerally in an amount of 0.01-1.0 mole, preferably 0.05-0.5 mole permole of the total amount of the diguanamine derivative, diguanamineand/or N-methyloldiguanamine derivative.

The above reaction can be conducted in the presence or absence of asolvent, with the reaction in the absence of any solvent beingpreferred. Nevertheless, it is possible to choose and use a solvent asdesired depending on the raw materials, reaction conditions and thelike. Any compound can be used as a solvent as long as it is inert tothe reaction. Examples of the solvent include, but are not limited to,aprotonic polar solvents such as ethers, dialkyl sulfoxides,alkyl-substituted acid amides and sulforans; esters; and ketones. Ofthese, ethers and aprotonic polar solvents are preferred.

Further, the above reaction can be conducted under normal pressure orunder naturally-occurring pressure or elevated pressure within a closedvessel. These reaction conditions can be chosen freely as needed.

Each of the hydroxyl-containing diguanamine derivatives andoxaalkyl-containing diguanamine derivatives according to the presentinvention can also be obtained by reacting the corresponding diguanamineof formula (1) or (2) with the corresponding alkylene carbonate such asethylene carbonate, propylene carbonate or 1,2-butylene carbonate at75°-250° C. in the presence or absence of a solvent while using a basiccatalyst such as potassium carbonate, sodium carbonate, caustic potash,caustic soda or pyridine.

The diguanamine derivatives according to the present invention can beobtained by any one of the preparation processes described above,although their preparation is not limited to these processes.

In the above process for the preparation of the diguanamine derivativesof this invention, the amine is preferably a compound represented by thefollowing formula:

    HO--Y.sub.9 --NH.sub.2

wherein Y₉ has the same meaning as defined above.

The compound represented by the formula HO--Y₉ --NH₂ is preferably acompound selected from the group consisting of 2-aminoethanol,1-aminopropan-2-ol, 2-aminobutan-1-ol, 3-aminopropan-1-ol,5-amino-3-oxapentan-1-ol and 4-aminophenol.

In the above preparation process, it is preferred to subject at leastone of the above diguanamine derivatives and at lease one of the aboveepoxides to an addition reaction.

It is also preferred to subject at least one diguanamine, which isselected from diguanamines represented by formula (1) or (2), and atleast one of the above epoxides to an addition reaction. Morepreferably, said at least one epoxide is selected from ethylene oxide orpropylene oxide.

The diguanamine derivatives according to the present invention areuseful for an extremely wide variety of applications as modifiers suchas flame retardants, heat resistance improvers, abrasion resistanceimprovers, thermal stabilizers and compatibilizing agents for resinsand, since they are excellent in the polymerizability and reactivitywith various compounds such as isocyanates, aldehydes, epoxides andcarboxylic acids, as resin raw materials, derivative raw materials,curing agents, chain extenders, crosslinking agents and the like, whichcan provide resins and derivatives excellent in heat resistance, flameretardancy, flexibility, toughness and the like. They can provide, forexample, flame-retardant resin compositions, polyurethane resincompositions, amino resin compositions, polyester resin compositions andthe like, all of which have superb properties.

The diguanamine derivatives according to the present invention canprovide a method for making a resin retardant to flame, which comprisesincorporating 3-50 wt. %, based on the resin, of at least onediguanamine derivative selected from the diguanamine derivativesdescribed above in the resin. It has also been found that combined useof the diguanamine derivative with at least one substance selected fromphosphoruses, isocyanuric acids and cyanuric acids or with anamino-containing compound can provide a flame-retarding method for aresin, which method makes it possible to obtain still improved flameretardancy owing to synergistic effects. Resin compositions which can beobtained by such flame-retarding methods are useful in a wide variety ofindustrial fields such as construction materials, electrical materials,materials for vehicles such as automotive vehicles, fiber materials andhousehold goods.

The above-described diguanamine derivatives, like the diguanaminesdescribed above, are useful in the flame retardation of resins.Conditions which are adopted upon employment of the diguanaminederivatives for the above application, for example, conditions for theircombined use with other additives, their proportions in resincompositions, applicable resins and the like are similar to those setout above for the diguanamines. Some of such conditions will next besummarized below by way of example.

The amount of the diguanamine derivative to be used can be chosen freelyas desired. However, it can be used generally in an amount of 3-50 wt.%, preferably 4-40 wt. % based on the resin.

As the phosphoruses, simple substances of phosphorus andphosphorus-containing compounds are both useful. Illustrative examplesinclude, but are not to be limited to, red phosphorus; phosphoric acidssuch as phosphoric acid, polyphosphoric acid, phosphorous acid andphosphonic acid; salts obtained by partially or fully neutralizing thesephosphoric acids with bases such as ammonia, amine, alkali metals andalkaline earth metals; phosphoric mono-, di- and tri-esters which mayoptionally contain one or more halogen atoms; salts of acidic phosphateesters with ammonia, amines, melamine, alkali metals and alkaline earthmetals; phosphite esters such as phosphorous triesters and phosphorousdiesters; phosphonate esters such as phosphonates esters, acidicphosphonate esters and salts thereof; phosphines such as phosphine,phosphine oxide and phosphonium salts; and sulfur-containing phosphoruscompounds such as dialkylthiophosphoric acids and salts thereof.Preferred are polyammonium phosphates represented by formula (NH₄)_(n+2)P_(n) O_(3n+1), n being an integer greater than 5, "Exolit 263" and"Exolit 422", trade names; products of Hoechst AG, phosphate esters andthe like. The amount of the phosphorus to be used is generally 5-40 wt.%, preferably 10-30 wt. % based on the resin.

Illustrative isocyanuric acids and cyanuric acids include, but are notlimited to, isocyanuric acid, trimethyl isocyanurate,tris(2-hydroxyethyl) isocyanurate, triphenyl isocyanurate, cyanuricacid, trimethyl cyanurate, tris(2-hydroxyethyl) cyanurate, diphenylcyanurate, triphenyl cyanurate, dimethyl phenyl cyanurate, andtriglycidyl cyanurate. The amount of the isocyanuric acids or cyanuricacids to be used can be chosen freely as needed. In general, they canhowever be used in an amount of 0.02-10 moles per mole of theabove-described diguanamine derivative.

When at least one compound selected from the above-describedamino-containing compounds is additionally used and incorporated in aresin, the flame retardancy of the resin can be improved further. Thecombined use of such an amino-containing compound is thereforepreferred. The amount of the amino-containing compound can be chosenfreely as needed. In general, it can however be used in an amount of0.01-10 wt. % based on the resin.

Further, it is particularly preferred to incorporate the above-describedphosphorus and amino-containing compound as flame-retarding aids in aresin.

The diguanamine derivatives described above can each be prepared byreacting at least one diguanamine, which is selected from thoserepresented by formula (1) or (2), with at least one amine. Use of acompound containing two or more amino groups as such an amine canprovide a diguanamine polymer depending on reaction conditions.

A flame-retarding method for a resin, which features incorporating inthe resin such a diguanamine polymer in an amount of 3-50 wt. % based onthe resin, can also substantially improve the flame retardancy of theresin like the above-described diguanamine derivatives, so that theflame-retarding method is extremely useful.

Each of the above-described diguanamine derivatives, when incorporatedin an amount of 0.01-5 wt. % based on a resin, can significantly improvethe thermal stability and ultraviolet light resistance of the resin andcan minimized coloration or discoloration of the resin during itsprocessing or forming at high temperatures. Such diguanamine derivativesare excellent in high-temperature stability and non-volatility andfeature easy handling, so that they can provide an excellent thermalstabilization method for resins.

According to such a thermal stabilization method of a resin, thediguanamine derivative can be used generally in an amount of 0.01-5 wt.%, preferably 0.02-1 wt. % based on the resin.

Resins to which the thermal stabilization method of the presentinvention can be applied are approximately the same as the-abovedescribed resins to which the above-described flame retarding method canbe applied.

These resins are preferably thermoplastic resins. At least one resinselected from the group consisting of polyphenylene ether resins,polyacetal resins, polyamide resins and polyolefin resins is morepreferred. A still more preferred polyolefin resin is at least one resinselected from the group consisting of polyethylene resin, polypropyleneresin and ethylene-propylene copolymers.

In the thermal stabilization method of such a resin, production of theresin composition and use of a phenolic antioxidant, an amine-baseantioxidant, a sulfur-containing antioxidant, a light stabilizer, anucleating agent, a phosphite antioxidant and/or other additives can beconducted, but are not limited to, in a similar manner to theabove-described flame-retarding method.

The present invention can also provide a method for compatibilizingresins, which comprises incorporating the above-described diguanaminederivative in a blend of at least two resins of different typescontaining at least one resin selected from polyamide resins,polyphenylene ether resins, polyimide resins and polyaramid resins.

The above compatibilization method is excellent, because it cansubstantially improve the compatibility of said at least two resins ofdifferent types and, moreover, can reduce coloration or discoloration ofthe blend during its processing or forming at high temperatures, and thederivative has excellent high-temperature stability, does not undergomuch sublimation, bleeding or the like and permits easy handling and hasgood dispersibility in melts of the polyamide resins, polyphenyleneether resins and the like.

In the resin compatibilization method according to the presentinvention, the diguanamine derivative can be used generally in an amountof 0.5-20 wt. % based on the total amount of the resins. Its amount canbe chosen freely as needed depending on the case.

As resins to which the resin compatibilization method of this inventioncan be applied, resins to which the above flame-retarding method isapplicable can be mentioned likewise. Specific examples of the at leasttwo resins of different types include, but are not limited to, one resinselected from polyamide resins, polyphenylene ether resins, polyimideresins and polyaramid resins and other resins, for example, a polyamideresin and ABS resin; a polyamide resin and a polyphenylene ether resin;and a polyimide resin and a polyphenylene ether resin; a polyamideresin, polyphenylene ether resin and other resins.

In the compatibilization method of such resins, production of the resincomposition and use of a phenolic antioxidant, an amine-baseantioxidant, a sulfur-containing antioxidant, a light stabilizer, anucleating agent, a phosphite antioxidant and/or other additives can beconducted, but are not limited to, in a similar manner to theabove-described flame-retarding method.

The diguanamine derivatives according to the present invention can eachprovide a polyurethane resin composition which comprises a polyolcomponent and an organopolyisocyanate component. The polyol componentcontains at least one diguanamine derivative selected from theabove-described hydroxyl-containing diguanamine derivatives andoxaalkyl-containing diguanamine derivatives. Such a resin compositioncan provide a material having excellent properties, for example,excellent mechanical properties such as flame retardancy, heatresistance, water resistance, abrasion resistance, flexibility,toughness and elasticity. The resin composition is useful for a widevariety of applications, for example, as soft and hard polyurethanefoams, paints, adhesives, plasticizers, sealants, caulking agents,film-waterproofing agents, floorings, polyurethane resin concretes,fiber treatments, sheets, films, rolls, tires, vibration-deadeningmaterials, belts, tubes, diaphragms, air brakes, soles, artificialleathers and elastic fibers. In particular, soft and hard polyurethanefoams are useful. It is to be noted that the resin composition is notlimited to such applications.

Illustrative specific embodiments of such applications include, but arenot limited to, preparation of a foaming polyurethane resin compositioncomprising the above-described polyol component and organopolyisocyanatecomponent, a foaming agent and a catalyst, followed by the production ofpolyurethane foam from the resin composition.

As an essential component of the polyol component, any derivative isuseful as long as it has been derived from one of the above-describeddiguanamines and containing one or more hydroxyl groups. Examples ofsuch derivatives include the above-described hydroxyl-containingdiguanamine derivatives and oxaalkyl-containing diguanamine derivatives.The number of hydroxyl group(s), the molecular weight, the type of theepoxide, the manner of addition, etc. can be chosen freely as desired.Incidentally, the polyol component may include one or more polyols otherthan the above-described essential component to an extent not impairingthe effects of the present invention. Illustrative examples of suchadditional polyols include, but are not limited to, water; alkyleneoxide adducts such as ethylene glycol, trimethylolpropane, glycerin,pentaerythritol, sorbitol and sugar; and alkylene oxide adducts such aspolyester polyols, acrylic polyols, butadiene polyols, phenolic polyols,halogen-containing polyols, phosphor-containing polyols,tris(2-hydroxyethyl) isocyanurate and tris(2-hydroxyethyl) melamine.

Exemplary organopolyisocyanate components include, but are not limitedto, 2,4-(2,6-)tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate,2,2'-dimethylphenylmethane-4,4'-diisocyanate,biphenyl-4,4'-diisocyanate, 1,5-nephthalene diisocyanate, tolidinediisocyanate, isophorone diisocyanate, p-phenylene diisocyanate,cyclohexane-1,4-diisocyanate, hexamethylene diisocyanate, xylylenediisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane-4,4'-diisocyanate, lysine diisocyanate, triphenylmethanetriisocyanate, tris-(isocyanate phenyl) thiophosphate, tetramethylxylenediisocyanate, lysine ester triisocyanates, 1,6,11-undecanetriisocyanate,1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-hexamethylenetriisocyanate, trimethylhexamethylene diisocyanate,azobenzene-4,4'-diisocyanate, 2-nitrobiphenyl-4,4'-diisocyanate, anddiphenylsulfone-4,4'-diisocyanate; and modified products, derivativesand the like of such isocyanates, such as their block isocyanates,isocyanate prepolymers, urethane adducts and isocyanurates.

The amount of the organopolyisocyanate to be used can be chosen freelyas needed. However, it is generally used in an amount equivalent to thehydroxyl number of the associated polyol component or in an amountgreater or smaller than the equivalent amount.

In the above-described foaming polyurethane resin composition, knownfoaming agents for urethane foams can each be used as a foaming agent.Illustrative of such foaming agents include, but are not limited to,reactive foaming agents such as water, nitroethane, acetaldoxime,formamidoboric acid, diazoaminobenzene and azobisisobutyronitrile; andnon-reactive foaming agents such as trichlorofluoromethane,dichlorodifluoromethane and trichlorotrifluoroethane. Examples of thecatalyst include, but are not limited to, known amine-base catalysts,organotin catalysts, alkali metal salts and alkali metal alcoholates.

Each diguanamine derivative according to the present invention canprovide an amino resin composition characterized in that the amino resincomposition comprises a reaction product, which has been obtained byreacting an amino compound including the diguanamine derivative with atleast one aldehyde, and at least one resin selected from amino resinsobtained by subjecting the above reaction product and alcohols toetherification, respectively. Such a resin composition can provide amaterial which is excellent in properties such as flame retardancy, heatresistance, flexibility, toughness and elasticity and is hence usefulfor a wide variety of applications, for example, as elastic foams suchas dividing walls (partitions) for buildings, heat insulating materialsand soundproofing materials for housings and transportation equipments,warm materials, and impact-resistant packaging materials; generalmolding for household appliances, automotive parts or components,various machines, and electrical parts and components; laminate formingmaterials; molding materials for SMC (sheet molding compounds) or BMC(bulk molding compounds); paints; and adhesives.

The present invention also provides polymeric microspheres characterizedin that the polymeric microspheres have been obtained by emulsifying anamino resin with a protective colloid, adding a curing agent to theemulsion so formed, and then polymerizing the resultant mixture. Theamino resin was obtained by reacting an amino compound containing atleast one diguanamine selected from the diguanamines represented byformula (1) or (2) with at least one aldehyde selected from thealdehydes. In addition, the present invention also provides coloredpolymeric microspheres obtained by coloring the above microspheres witha colorant as well as a method for making a resin retardant to flame,which comprises incorporating 3-50 wt. %, based on the resin, of theuncolored or colored polymeric microspheres.

The proportion of the diguanamine in the polymeric microspheresaccording to the present invention can be chosen freely depending on thedesired properties. To provide an amino resin having good solubility ordispersibility in solvents such as water and also polymer microsphereshaving excellent heat resistance, solvent resistance, weatherability,impact resistance and abrasion resistance, it is preferred to controlthe proportion of the diguanamine in an amount of at least 40 wt. %,more desirably at last 60 wt. % based on the amino compound. The aminocompound can additionally include one or more compounds other than theabove-described diguanamines. Illustrative of such compounds includemelamine, N-methylmelamine, benzoguanamine, acetoguanamine, cyclohexanecarboguanamine, cyclohexene carboguanamine, norbonane carboguanamine,norbornene carboguanamine, dicyandiamide, urea, thiourea, guanidine,urethane, phenol, p-methylphenol, nonylphenol, resoles, aniline,tetramethylenediamine, furfural, furfuryl alcohol, p-toluenesulfonamide,o-toluenesulfonamide, benzenesulfonamide, tetralinsulfonamide,carboxylic amides, sulfuryl amide, and lower polymer of phosphorusdiamide nitride. Such additional compounds can be used in any totalamount insofar as the significance of the use of the amino compound inthe present invention is not impaired, but preferably in a total amountsmaller than 60 wt. % of the amino compound.

Examples of the aldehyde usable for the production of the polymericmicrospheres according to the present invention include formaldehydessuch as formaldehyde, paraformaldehyde, hexamethylenetetramine,methylhemiformal, butylhemiformal and formaldehyde-sodium bisulfiteadduct; glyoxal; acetaldehyde; trimethylol acetaldehyde; acrolein;benzaldehyde; furfural; phthalaldehyde; and terephthaldehyde. Amongthese, formaldehydes and glyoxal are preferred, with an aqueous solutionof formaldehyde and paraformaldehyde being more preferred. Suchformaldehyde(s) preferably account for at least 50 wt. % of thealdehyde. The aldehyde can be used generally in an amount of 1.5-16moles, preferably 2.0-10 moles, more preferably 2.5-6.0 moles per moleof the amino compound.

Although no particular limitation is imposed on the manner of obtainingthe amino resin for use in the production of the polymeric microspheresaccording to the present invention, several processes may be mentionedas examples. A liquid mixture, which has been formed by stirring andmixing the above-described amino compound and aldehyde in one or moresolvents such as water, alcohols and/or aromatic compounds, is subjectedto an addition reaction at 30°-80° C. and pH 8-13, whereby anN-methyloldiguanamine is obtained. As an alternative, such a liquidmixture is subjected to addition condensation under high alkalineconditions of pH 13 or higher or under conditions of pH 8 or lower,whereby a primary condensate N-methyloldiguanamine is obtained. As afurther alternative, the N-methyloldiguanamine or primary condensateN-methyloldiguanamine so obtained is caused to undergo furthercondensation at pH 1-6 and 30°-80° C. so that a condensate is obtainedwith a condensation degree increased to an appropriate extent. As astill further alternative, the N-methyloldiguanamine or primarycondensate N-methylolguanamine obtained above can be subjected toetherification with an alcohol having 1-20 carbon atoms at pH 1-6 and30°-90° C. to obtain a partially etherified product. This partiallyetherified product can also be used as an amino resin in the presentinvention. Use of such a partially etherified product is generally notpreferred, because it tends to result in poor emulsification and/orcuring upon production of polymeric microspheres and/or in polymericmicrospheres reduced in impact resistance, solvent resistance and thelike. Such a partially etherified product may provide polymericmicrospheres which are still useful for certain applications. It is tobe noted that the manner of obtaining an amino resin useful in theproduction of polymeric microspheres according to this invention is notlimited to the processes exemplified above.

Examples of the protective colloid employed for the production ofpolymeric microspheres according to the present invention include, butare not limited to, alkali metal salts of polyacrylic acids, alkalimetal salts of styrene-maleic acid copolymers, alkali metal salts ofisobutylene-maleic acid copolymers, alkali metal salts ofp-styrenesulfonic acid polymer, alkali metal salts ofsulfonic-acid-modified amino resins, saponified products of vinylacetate polymers such as polyvinyl alcohol, and polyvinyl pyrrolidone,with saponified products of vinyl acetate polymers being preferred. Theamount of the protective colloid to be used can be chosen freely asdesired depending on the desired properties, sphere size and the like.In general, however, the protective colloid can be used in an amount of0.2-25 wt. %, preferably 1.0-15 wt. % based on the amino resin. Noparticular limitation is imposed on the manner of emulsification. Anymethod useful in emulsifying resins in prior art can be applied. Forexample, the amino resin can be emulsified by agitating it with astirring blade in the form of an anchor, a propeller, a turbine or thelike or in an agitator such as a colloid mill, dispersion mill orhomomixer. It is however to be noted that the emulsification of theamino resin is not limited to the above-exemplified methods.

As the curing agent usable in the production of the polymericmicrospheres according to the present invention, any compounds can beused as long as they can release or form protons under productionconditions. Illustrative curing agents include, but are not limited to,mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acidand nitric acid; carboxylic acids such as formic acid, benzoic acid,phthalic acid, acetic acid, α-chloroacetic acid, trifluoroacetic acid,propionic acid, oxalic acid, lactic acid, amino acids and salicylicacid; sulfonic acids such as benzenesulfonic acid, p-toluenesulfonicacid, o-toluenesulfonic acid and dodecylbenzenesulfonic acid; ammoniumsalts such as ammonium chloride, ammonium sulfate, ammonium phosphate,ammonium dihydrogenphosphate, diammonium hydrogenphosphate, ammoniumnitrate, ammonium formate, ammonium acetate, ammoniump-toluenesulfonate, ammonium sulfamate and diammonium imidosulfonate;chloroacetamides; and water-soluble metal salts of metals such as zinc,magnesium, calcium and aluminum with acids such as nitric acid, sulfuricacid and phosphoric acid, with sulfonic acids being preferred. Thecuring agent can be used in an amount of 0.01-5 wt. %, preferably 0.05-3wt. % based on the above-described amino resin. Amounts smaller than0.01 wt. % lead to insufficient curing and hence to polymericmicrospheres reduced in impact resistance, solvent resistance and thelike, whereas amounts greater than 5 wt. % can hardly achieveemulsification in a good state. Amounts outside the above range aretherefore not preferred.

In the present invention, polymeric microspheres colored with a colorantare also provided. The colorant can be chosen freely depending on theapplication or the like of the polymeric microspheres. A dye such as awater-soluble dye or an oil-soluble dye, a pigment or the like is usefulas the colorant. Illustrative examples of such a colorant include, butare not limited to, basic dyes such as Rhodamine B, Rhodamine 6GCF,Methylviolet B, Aizen Astraphloxine FF, Malachite Green A, Victoria PureBlue RB and Methylene Turquoise J; acidic dyes such as Acilan Scarlet A,Acid Red XB, Eosine, Lissamine Flayin FF, Alizarine Fast Violet 2RC andSulforhodamine G; cationic dyes such as Astrazone Pink FG, Astrazone Red6B, Aizen Cathilon Brilliant Yellow 5GLH and Aizen Cathilon Orange RH;solvent-soluble dyes such as Rhodamine B Base, Azosole Brilliant Yellow8GF, Azosole Brilliant Yellow 6GF and Azosole Brilliant Blue B;fluorescent brightening dyes such as Uvi-Tex ERN and Tipanol PCR; andpigments such as Heliogen Green 6G and Heliogen Blue LBGM. No particularlimitation is imposed on the manner of coloration with such a colorantand any method employed upon coloring resins in prior art or the likecan be applied. It is however preferred to add a colorant at a stagefrom a time point, at which conversion of a product into a hydrophobicform is initiated, to the end of production of polymeric microspheres inthe production of the polymeric microspheres. The amino resin can becolored, for example, by adding the colorant in the course of theproduction of the amino resin or after the completion of the productionor by adding the colorant after the amino resin has been emulsifiedusing a protective colloid. It is however to be noted that the manner ofcoloration is not limited to the methods exemplified above.

The polymeric microspheres according to the present invention cancontain, to an extent not impairing the effects of the presentinvention, other additives, for example, flame retardants, antistaticagents, antihazing agents, lubricants, fluorescent agents, plasticizers,mildewproofing agents, bacteriocides, antioxidants, ultraviolet lightabsorbers, fillers, metal inactivating agents and/or the like as needed.

According to the process of the present invention for the production ofpolymeric microspheres, the polymeric microspheres can be obtained witha desired sphere size, generally of 0.1-20 micrometers, and desiredproperties. It is also useful to subject the resulting polymericmicrospheres to post-treatment, for example, to separate them byfiltration, centrifugal separation or the like, followed by waterwashing, drying and the like, or to subject them to heat treatment at100°-250° C. for 0.5-5.0 hours. Such post-treatment can be chosen freelydepending on the application or the like.

The polymeric microspheres according to the present invention areexcellent in heat resistance, solvent resistance, weatherability,abrasion resistance, flame retardancy and the like, and are useful for awide variety of applications as modifiers, compatibilizing agents orfillers for thermoplastic resins, thermosetting resins and rubbers;blocking preventives for plastic films, cellophane films and inks;abrasion resistance improvers or stress relaxing agents for epoxy resinsand phenol resins; flowability improvers for plastics and rubbers; heatresistance improvers, thermal stability improvers, elasticity (e.g.,impact resistance) regulating agents or slidability improvers forplastics, films and sheets; viscosity regulating agents for paints, inksand adhesives; paper quality modifiers; dispersibility improvers oranti-caking agents for powders; strippable adhesion imparting agents foradhesive tapes and sticking plasters; dispersants or dispersionstabilizers for pigments and the like; delustering agents; powderylubricants; car waxes; forming aids for sintering materials;concavity/convexity imparting agents; mold release agents; strippabilitymodifiers; transparency and/or gloss improvers for plastics; additivesfor cosmetics; pigments for cosmetics; scrubbing agents; drying paints;ink conditioners; pressure-sensitive paper conditioners; spacers forliquid crystal panels; special inks for recording materials such astoner; resinous colorants for water-base and oil-base paints;fluorescent paints; traffic paints; resinous colorants for printing inkssuch as gravure inks, offset inks and silk screening inks; and resinouscolorants or pigment printing agents for plastics and fibers.

The above-described polymeric microspheres, like the diguanaminesdescribed above can provide a method for a resin retardant to flame.Conditions which are adopted upon employment of the polymericmicrospheres for the above application, for example, conditions fortheir combined use with other additives, their proportions in resincompositions, applicable resins and the like are similar to those setout above for the diguanamines. Some of such conditions will next bedescribed by way of example.

In the flame-retarding method for a resin which features incorporationof the above polymeric microspheres, it is preferred to incorporate atleast one phosphorus selected from phosphoruses consisting of simplesubstances of phosphorus and phosphorus-containing compounds. Preferredexamples of such phosphoruses include red phosphorus, phosphoric acid,polyphosphoric acid, phosphorous acid, phosphonic acid, phosphate salts,polyphosphate salts, phosphite salts, phosphonate salts, phosphateesters, phosphite esters, phosphonate esters, phosphines andsulfur-containing phosphorus compounds. Such polyphosphate salts arepreferably ammonium polyphosphates represented by formula (NH₄)_(n+2)P_(n) O_(3n+1) in which n represents an integer greater than 5. Thephosphoruses can be used in an amount of 5-40 wt. %, preferably 10-30wt. % based on the resin.

It is also preferred to incorporate at least one compound selected fromthe isocyanuric acids and cyanuric acids represented by formulas (9) and(10), respectively. The proportion the isocyanuric acid or the cyanuricacid to be used can be chosen freely as needed but can generally rangefrom 0.02 mole to 10 moles per equivalent of the diguanamine skeleton inthe polymeric microspheres.

In the above-described flame-retarding method, it is possible andpreferred to improve the flame retardancy of the resin further by usingan amino-containing compound in combination with the diguanamine. Theamount of such an amino-containing compound can be chosen freely asneeded but can generally range from 0.01 wt. % to 10 wt. % based on theresin.

Further, it is particularly preferred to incorporate the above-describedphosphoruses and amino-containing compound together in a resin.

Preferred examples of the resin are thermoplastic resins andthermosetting resins. The thermoplastic resins are preferably polyolefinresins, polyamide resins, styrene resins, polyphenylene ether resins,saturated polyester resins, polycarbonate resins, polyacetal resins andacrylic resins. The thermosetting resins are preferably unsaturatedpolyester resins, diallyl phthalate resins, epoxy resins and urethaneresins.

A method for making a resin retardant to flame--which comprisesincorporating 3-50 wt. %, based on the resin, of a product obtained byreacting at least one compound selected from the diguanaminesrepresented by formula (1) or (2) and the diguanamine derivativesrepresented by formula (11) or (12) with at least one compound selectedfrom the above-described aldehydes, a product obtained by etherifyingthe former product with an alcohol, or a condensate or polymerthereof--can significantly improve the flame retardancy of the resinlike the flame-retarding methods described above and is therefore anextremely useful method.

In the above-described method, the conditions adopted for theabove-described flame-retarding methods making use of the diguanamine,for example, the conditions for the combined use of the phosphoruses,the isocyanuric acids, the cyanuric acids and/or the amino-containingcompounds, their proportions in resin compositions, applicable resinsand the like can be applied likewise.

The use of the diguanamines, the diguanamine derivatives and theirpreparation process and use, and the polymeric microspheres and theiruse, all of which have been described above and pertain to the presentinvention, can bring about the following effects as advantages of thepresent invention.

According to the flame-retarding method of the present invention for aresin, the flame retardancy of the resin can be significantly improvedowing to the incorporation of the novel diguanamine having the specificstructure in the resin. The diguanamine has better heat resistance andits sublimation, bleeding or the like is not observed compared withmelamines. The flame-retarding method has excellent effects for theimprovement of the flame retardancy of the resin, because the resin sotreated is extremely good in char formability or the like, developsextremely little sagging or dripping of oil droplets or a melt and doesnot give off extremely noxious gas during burning. Further, the combineduse of the diguanamine with the phosphoruses, the isocyanuric acids, thecyanuric acids and/or the amino-containing compounds can provide theflame-retarding method for a resin, which can obtain still improvedflame retardancy because of synergistic effects. These methods have madeit possible to expand the application field of resins still further. Thepresent invention is therefore extremely important from the industrialstandpoint.

The thermal stabilization method of the present invention for a resin,on the other hand, features the incorporation of the novel diguanamineof the specific structure in the resin, so that the resin issignificantly improved in ultraviolet light resistance, thermalstability and the like. Even when the resin so treated is molded orotherwise formed at high temperatures, coloration or discoloration ofthe resin is minimized, thereby demonstrating improved thermalstability. Further, even when used for a long time at relatively hightemperatures, deterioration is reduced so that the retention of physicalproperties has been improved substantially. The thermal stabilizationmethod is extremely effective for the stability to heat, light and thelike and can exhibit its effects for a long time, without developing anysecondary disadvantages. In addition, the thermal stabilization methodcan substantially overcome the drawback that degradation ordeterioration of the resin is promoted by heavy metal ions such ascopper ions. The above thermal stabilization is therefore very effectivefor the improvement of the thermal stability of the resin. This methodhas made it possible to expand the application field of the resin stillfurther. The present invention is therefore extremely important from theindustrial standpoint.

According to the compatibilization method of the present invention, thenovel diguanamine having the specific structure is incorporated in ablend of two or more resins of different kinds. This method is extremelyeffective for the improvement of the compatibility of the two or moreresins of different kinds, because the compatibility of the resins canbe significantly improved and, moreover, the blend so treated does notundergo much coloration or discoloration upon its processing or formingat high temperatures, the diguanamine is excellent in high-temperaturestability and non-volatility, undergoes minimized sublimation, bleedingor the like, features easy handling and preparation and has gooddispersibility in melts of polyamide resins, polyphenylene ether resinsand the like, and the resin so treated is also improved in thermalstability. This method has made it possible to expand the applicationfield of the resin still further. The present invention is thereforeextremely important from the industrial standpoint.

Each diguanamine derivative according to the present invention featuresthat it can impart excellent heat resistance, flame retardancy,weatherability, flexibility and toughness to resins, contains activehydroxyl and imino groups capable of exhibiting excellent reactivitywith compounds having one or more of various functional groups such asisocyanate, carboxyl, epoxy and aldehyde group and the like, and permitsselection of the number of functional group(s) from a wide range, forexample, eight functional groups containing an active hydrogen atoms.Further, the diguanamine derivative is also excellent in properties suchas curing property and high-hardness-imparting property so that it canprovide compounds, resins, compositions and the like having excellentproperties. The diguanamine derivative is therefore useful for anextremely wide variety of applications. In addition, the process of thepresent invention for the preparation of the diguanamine derivativecomprises reacting the novel diguanamine having the specific structurewith the diamine or the above diguanamine and/or diguanamine derivativewith the epoxide under the particular conditions so that the targetderivative can be obtained easily in a high yield. The preparationprocess is therefore excellent.

The diguanamine derivatives according to the present invention haveexcellent effects such that, when incorporated in a resin to make theresin retardant to flame, they can substantially improve the flameretardancy of the resin, and the resin so treated is extremely good inchar formability or the like, develops no substantial sagging ordripping of oil droplets or a melt and good in self-extinguishment. Thecombined use of the phosphoruses, the isocyanuric acids, the cyanuricacids and/or the amino-containing compounds in the above-describedmethod can provide a flame-retarding method which can impart stillimproved flame retardancy owing to synergistic effects. The presentinvention is therefore extremely important from the industrialstandpoint.

Each diguanamine derivative described above has excellent effects suchthat, when incorporated in a resin to thermally stabilize the resin, thederivative can significantly improve the thermal stability andultraviolet light resistance of the resin, can minimize coloration ordiscoloration of the resin upon processing or forming it at hightemperatures, has superb high-temperature stability, does not undergosubstantial sublimation, bleeding or the like, can be handled easily,and has good dispersibility in a melt of the resin. Further, when thediguanamine derivative is incorporated in a blend of two or more resinsof different kinds to compatibilize the resins, the diguanaminederivative shows excellent effects such that it can substantiallyimprove the compatibility of the different resins and, moreover, it canminimize coloration or discoloration of the resins upon processing orforming it at high temperatures, does not undergo substantialsublimation, bleeding or the like, can be handled easily, and has gooddispersibility in a melt of the resin. These resin modification methodsmaking use of the above-described diguanamine derivative according tothe present invention have made it possible to expand the applicationfield of the resin still further. The present invention is thereforeextremely important from the industrial standpoint.

The above-described diguanamine derivatives can each be incorporatedtogether with an organoisocyanate component to provide a polyurethaneresin composition. Such a resin composition can provide a materialexcellent in properties, for example, mechanical properties such asflame retardancy, heat resistance, water resistance, abrasionresistance, flexibility, toughness and elasticity. The present inventionis therefore extremely important from the industrial standpoint.

The polymeric microspheres according to the present invention can beobtained by emulsifying an amino resin with a protective colloid, addinga curing agent to the emulsion so formed, and then polymerizing theresultant mixture. The amino resin has been obtained by reacting anamino compound, which contains the novel diguanamine having theparticular structure, with the aldehyde. The polymeric microspheres areexcellent in heat resistance, solvent resistance, weatherability, impactresistance and abrasion resistance. When colored with a colorant,polymeric microspheres useful as a resinous colorant can be provided.Such polymeric microspheres are extremely useful for a wide variety ofapplications, for example, as resin modifiers (such as fillers, heatresistance improvers, flame retardancy improvers, thermal stabilityimprovers, abrasion resistance improvers, and elasticity regulatingagents) for thermoplastic resins, thermosetting resins and rubbers;antiblocking agents for plastic films, cellophane films and inks;viscosity regulating agents for paints, inks, adhesives and cosmetics;and surface modifiers. The present invention is therefore extremelyimportant from the industrial standpoint.

The polymeric microsperes according to the present invention haveexcellent effects such that, when incorporated in a resin to make theresin retardant to flame, they can substantially improve the flameretardancy of the resin, they do not undergo sublimation, bleeding orthe like as opposed to melamines, and the resin so treated is good inheat resistance and extremely good in char formability or the like,develops no substantial sagging or dripping of oil droplets or a melt,and does not give off extremely noxious gas or the like upon burning.The combined use of the phosphoruses, the isocyanuric acids, thecyanuric acids and/or the amino-containing compounds in theabove-described method can provide a flame-retarding method which canimpart still improved flame retardancy owing to synergistic effects.This flame-retarding method has made it possible to expand theapplication field of the resin still further. The present invention istherefore extremely important from the industrial standpoint.

THIRD INVENTION GROUP Technical Field

This invention relates to a thermosetting molding composition extremelyuseful, for example, as general molding materials for householdappliances, automotive parts or components, various machines andelectrical parts or components, laminate-molding materials, and moldingmaterials for sheet and bulk molding processes for the formation offiber-reinforced plastics. This invention is also concerned with athermosetting expansion-forming composition useful as anexpansion-forming material for dividing walls (partitions) in buildings,a heat-insulating, soundproofing or low-temperature shielding materialfor housing and transportation equipments, a warm material for tanks, animpact-resistant packaging material, or a filler. The term "forming" asused herein should be interpreted in a broad sense so that it embracesnot only molding but also other forming techniques such as extrusion.

BACKGROUND ART Thermosetting Molding Material

In general, the term "thermosetting molding material" means a materialwhich has been obtained by impregnating a thermosetting resin with acuring agent, a filler, a mold release agent, a dye or pigment, athickening agent and the like as needed so that it can be convenientlyformed into a desired shape by heating and pressing it as needed. Suchmaterials are advantageous inter alia in that they can be directlyformed into products of various shapes, the products so formed have agood surface finish, formed products of a desired color can be obtainedby dispersing the corresponding dye or pigment in advance and no coatingwork is needed, so that they are useful as industrial materials. Knownexamples of the thermosetting resin include phenol resins, melamineresins, and unsaturated polyester resins.

Among these molding materials, phenol resins are excellent in electricalinsulating property and cracking resistance but, as their defects, arepoor in weatherability and high-temperature discoloration resistance aswell as arc resistance and anti-tracking properties, so that theirapplications are considerably limited. Melamine resins are excellent incolorability, surface hardness, anti-tracking properties and the likebut exhibit insufficient flowability upon molding. Molded productsobtained from melamine resins lack flexibility and have poor impactresistance and, as their defects, tend to develop seasoning cracks andmetal insert cracks. Unsaturated polyester resins, on the other hand,are excellent in flexibility, water resistance and the like but, astheir defects, lack heat resistance and at relatively high temperatures,chemical resistance and are susceptible to burning. Accordingly, thesethermosetting molding materials are still dissatisfactory for practicaluse and substantial limitations are imposed thereon technically andeconomically.

With a view to overcoming the above-described drawbacks of moldingmaterials making use of such thermosetting resins, the present inventorshave conducted an extensive investigation. As a result, it has beenfound that use of an amino resin--which is obtained by reacting analdehyde with an amino compound containing a novel specific diguanaminetotally different in structure and properties from conventionally knowncompounds--features easy and simple production and handling of the resinand can conveniently provide a thermosetting molding composition whichis easy to handle and has excellent flowability upon forming, and easyformation of products of various shapes having excellent weatherability,heat resistance, electrical characteristics, mechanical properties andthe like, leading to the present invention.

Thermosetting Expansion-Forming Composition

Further, this invention also relates to a thermosettingexpansion-forming composition.

It is conventionally known that a foam can be obtained from a resincomposition, which contains a primary condensate obtained by reactingmelamine, urea or the like with formaldehyde, by causing the resincomposition to expand and cure.

In such a resin composition, use of a primary condensate of melamine orthe like involves the drawbacks that the resulting foam is hard andbrittle and tends to break upon processing or forming. It has beenproposed to improve its elasticity and shatter resistance by introducinga polyol or the like. This proposal is however accompanied by drawbackssuch that the resulting foam is still in sufficient in elasticity, shaperestorability and the like and is significantly reduced in flameretardancy, heat resistance and the like. It has also been proposed toobtain a foam of relatively good mechanical properties, heat insulatingproperty and the like by exposing a resin composition, which contains aprimary condensate of melamine or the like having a relatively largecondensation degree, to a high frequency wave and causing it to expandand cure. A primary condensate of melamine or the like having a smallcondensation degree, however, involves drawbacks such that it leads to afoam significantly reduced in mechanical properties, heat insulatingproperty and the like and can hardly provide any good foam and moreovera liquid formulation of the primary condensate tends to form aprecipitate and has poor workability and storage stability, although thesolubility and dispersibility in a solvent are improved to some extents.A large condensation degree, on the other hand, can provide a foamhaving relatively good mechanical properties and heat insulatingproperty, but such a large condensation degree is accompanied bydrawbacks such that the resulting foam has very poor solubility ordispersibility in a solvent such as water. Achievement of an increasedcondensation degree upon production of a resin results in drawbacks suchthat the solubility and compatibility are substantially lowered and theresin may separate during the reaction, whereby it is extremelydifficult to obtain any preferred primary condensate. With a view toimproving these drawbacks and difficulty, it has also been proposed toevaporate a liquid mixture of a resin having a relatively smallcondensation degree to dryness, to allow the resin to age to have alarger condensation degree and then to redissolve and disperse theresin. These processes however require complex production steps, needsubstantial consumption of heat and are disadvantageous economically.Moreover, the above methods are accompanied by drawbacks such thatsubstantial difficulties are encountered for the control of thecondensation, they require additional steps for re-dissolution,dispersion or the like of the resin and are cumbersome, the distributionof condensation degree is wide, thereby making it difficult to achievefull dissolution, dispersion or the like the resin, significantlimitations are imposed on the conditions for the production of foams,storage stability and workability are insufficient, the resulting foamcan hardly be controlled in performance and quality, and the performanceis not still sufficient and the application is considerably limited.

It has also been proposed to obtain a foam with improved elasticity andflexibility from a resin composition containing a primary condensate orurea or the like. Although this method can provide a foam havingsomewhat improved mechanical properties, it is accompanied by drawbackssuch that the resulting foam is considerably inferior in flameretardancy, heat resistance and the like and its application istherefore very limited.

These resin compositions have the above-described drawbacks and arestill insufficient for practical use. Substantial limitations have hencebeen imposed technically and economically on them.

With a view to overcoming the above-described drawbacks of such resincompositions and foams obtained therefrom, the present inventors haveconducted an extensive investigation. As a result, it has been foundthat use of an amino resin--which is obtained by reacting an aldehydewith an amino compound containing a novel specific diguanamine differentin structure and properties from conventionally known compounds--or amodified amino resin obtained by modifying the above amino resin with asulfonic acid can provide an expansion-forming composition featuringextremely good solubility as dispersibility in a solvent such as water,storage stability and the like, easy and simple production and handlingof the resin and composition, and the ability to provide a foamexcellent in flame retardancy and mechanical properties. It has alsobeen found that an elastic foam excellent in heat insulating property,soundproofing property, flame retardancy, heat resistance, impactresistance, vibration resistance, processability, formability,mechanical properties and the like and useful for a wide variety ofapplication can be provided. These findings have led to the presentinvention.

DISCLOSURE OF THE INVENTION

An object of the present invention is to improve the drawbacks of theconventional thermosetting molding compositions and thermosettingexpansion-forming compositions as described above. This inventiontherefore provides:

(a) a thermosetting molding composition comprising an amino resin and areinforcing material, said amino resin having been obtained by reactingat least one aldehyde with an amino compound comprising at least onediguanamine selected from diguanamines represented by the followingformula (1): ##STR25## wherein the bonding sites of the4,6-diamino-1,3,5-triazin-2-yl groups are the 2,5- or 2,6-positions, orby the following formula (2): ##STR26## wherein the bonding sites of the4,6-diamino-1,3,5-triazin-2-yl groups are the 1,2-, 1,3- or1,4-positions; and

(b) a thermosetting molding composition comprising an amino resin and areinforcing material, said amino resin having been obtained by reactingat least one aldehyde with an amino compound comprising at least onediguanamine derivative selected from diguanamine derivatives representedby the following formula (11): ##STR27## wherein the bonding sites ofthe 1,3,5-triazin-2-yl groups are the 2,5- or 2,6-positions, and Y₁, Y₂,Y₃, Y₄, Y₅, Y₆, Y₇ and Y₈ are the same or different and individuallyrepresent a substituent selected from the group consisting of a hydrogenatom and groups containing at least two carbon atoms, with the provisothat at least one of Y₁, Y₂, Y₃, Y₄, Y₅, Y₆, Y₇ and Y₈ is a groupcontaining at least two carbon atoms, or by the following formula (12):##STR28## wherein the bonding sites of the 1,3,5-triazin-2-yl groups arethe 1,2-, 1,3- or 1,4-positions and Y₁, Y₂, Y₃, Y₄, Y₅, Y₆, Y₇ and Y₈have the same meanings as defined in formula (11).

The present invention also provides:

(c) a thermosetting expansion-forming composition comprising an aminoresin, an emulsifier, a foaming agent and a curing agent, said aminoresin having been obtained by reacting at least one aldehyde with anamino compound comprising at least one diguanamine selected from thediguanamines represented by formula (1) or (2);

(d) a thermosetting expansion-forming composition comprising an aminoresin, an emulsifier, a foaming agent and a curing agent, said aminoresin having been obtained by reacting at least one aldehyde with anamino compound comprising at least one diguanamine derivative selectedfrom the diguanamines derivatives represented by formula (11) or (12);and

(e) a thermosetting expansion-forming composition comprising a modifiedamino resin, an emulsifier, a foaming agent and a curing agent, saidmodified amino resin having been obtained by sulfonating the amino resinset out above under (c) or (d).

Among the above-described diguanamine derivatives according to thepresent invention, preferred are hydroxyl-containing diguanaminederivatives represented by formula (11) or (12) in which Y₁, Y₂, Y₃, Y₄,Y₅, Y₆, Y₇ and Y₈ individually represent a substituent selected from thegroup consisting of a hydrogen atom and groups represented by HO--Y₉ --,Y₉ being a divalent group containing at least two carbon atoms. Alsopreferred are hydroxyl diguanamine derivatives in which HO--Y₉ -- is agroup selected from the group consisting of 2-hydroxyethyl,2-hydroxypropyl, 1-hydroxymethylpropyl, 3-hydroxypropyl,5-hydroxy-3-oxapentyl and 4-hydroxyphenyl groups. Also preferred areoxaalkyl-containing diguanamine derivatives represented by formula (11)or (12) in which at least one of Y₁, Y₂, Y₃, Y₄, Y₅, Y₆, Y₇ and Y₈represents a group selected from the group consisting of groupsrepresented by formula (13) or (14). More preferably, Y₁₀ in formula(13) or (14) is at last one group selected from ethylene and propylene.

More preferred are diguanamine derivatives represented by formula (11)or (12) in which Y₂, Y₄, Y₆ and Y₈ are individually a hydrogen atom andY₁, Y₃, Y₅ and Y₇ are individually a substituent selected from the groupconsisting of a hydrogen atom, the above-described groups HO--Y₉ --, andgroups represented by formulas (13) and (14) respectively.

The proportion of the diguanamine or the diguanamine derivative in thethermosetting molding composition according to the present invention canbe chosen freely depending on the desired properties. To provide athermosetting molding composition which can be produced easily andsimply, has excellent flowability upon molding, permits easy formationof products of various shapes and are excellent in weatherability, heatresistance, flame retardancy, electrical characteristics, mechanicalproperties and the like, it is preferred to control the proportion ofthe diguanamine or the diguanamine derivative in an amount of at least40 wt. % more desirably at least 80 wt. % based on the amino compound.

To obtain a liquid amino resin formulation, which has better storagestability and can provide formed products superior in adhesionproperties, mechanical properties and the like, by using the diguanaminederivative, the diguanamine derivative should amount preferably to0.1-70 wt. %, more preferably 1-30 wt. % of the amino compound.

The amino compound can additionally include one or more compounds otherthan the above-described diguanamines or diguanamine derivatives.Illustrative of such compounds include melamine, N-methylmelamine,benzoguanamine, acetoguanamine, cyclohexanecarboguanamine,cyclohexenecarboguanamine, norbonanecarboguanamine,norbornenecarboguanamine, dicyandiamide, urea, thiourea, guanidine,urethane, phenol, p-methylphenol, nonylphenol, resoles, aniline,tetramethylenediamine, furfural, furfuryl alcohol, p-toluenesulfonamide,o-toluenesulfonamide, benzenesulfonamide, tetralinsulfonamide,carboxylic amides, sulfuryl amide, and lower polymer of phosphorusdiamide nitride. Such additional compounds can be used in any totalamount insofar as the significance of the use of such an amino compoundas described above in the present invention is not impaired, butpreferably in a total amount smaller than 60 wt. % of the aminocompound.

Usable examples of the aldehydes usable in the present invention includeformaldehydes such as formaldehyde, paraformaldehyde,hexamethylenetetramine, methylhemiformal, butylhemiformal andformaldehyde-sodium bisulfite adduct; glyoxal; acetaldehyde; trimethylolacetaldehyde; acrolein; benzaldehyde; furfural; phthalaldehyde; andterephthaldehyde. Among these, an aqueous solution of formaldehyde andparaformaldehyde are preferred. Such aldehydes can be used generally inan amount of 1.0-16 moles, preferably 1.5-8.0 moles, more preferably2.0-7.5 moles per mole of the amino compound.

Although no particular limitation is imposed on the manner of obtainingthe amino resin for use in the present invention, several processes maybe mentioned as examples. A liquid mixture, which has been formed bystirring and mixing the above-described amino compound and aldehyde in asolvent system such as one or more of water, alcohols, ethers and/oraromatic compounds, is subjected to an addition reaction at 30°-80° C.and pH 8-13, whereby an N-methyloldiguanamine is obtained. As analternative, such a liquid mixture is subjected to addition condensationunder high alkaline conditions of pH 13 or higher or under conditions ofpH 8 or lower, whereby a primary condensate of an N-methyloldiguanamineis obtained. As a further alternative, the N-methyloldiguanamine or theprimary condensate of the N-methyloldiguanamine so obtained is caused toundergo further condensation at pH 1-6 and 50°-100° C. so that acondensate is obtained with an increased condensation degree. As a stillfurther alternative, the amino resin obtained by conducting a reactionas described above is heated at 60°-150° C. under normal or reducedpressure to eliminate water originated from the aldehyde as the rawmaterial, water formed by the condensation reaction, the solvent and thelike. The amino resin so obtained is also useful. It is however to benoted that the manner of production of the amino resin is not limited tosuch processes and conventionally-known processes can also be usedlikewise. In some instances, conditions such as the condensation degreeof the amino resin, the solvent and the pH can be chosen as needed.

The thermosetting molding composition according to the present inventionfeatures the inclusion of the above-described amino resin and areinforcing material as essential components. The combined use of suchan amino resin and a reinforcing material can provide a thermosettingmolding composition having excellent properties extremely difficult toobtain with conventional melamine-type amino resins, such as excellentflowability upon molding, weatherability and adhesion properties withthe reinforcing material and, owing to synergistic effects, stillimproved heat resistance, flame retardancy, mechanical properties andthe like.

Illustrative examples of the reinforcing material include, but are notlimited to, glass fibers such as E-glass fibers, C-glass fibers, A-glassfibers, S-glass fibers, and glass fibers obtained by finishing suchglass fibers with a coupling agent; glass fiber products such as glassrovings, glass cloths, chopped glass strands, and chopped glass strandmats, all obtained from such glass fibers as described above;polycrystalline fibers such as a variety of carbon fibers, aluminafibers, zirconia fibers and boron nitride fibers; composite fibers suchas boron fibers, silicon carbide fibers, polytitanocarbosilane fibersand calcium titanate fibers; organic fibers such as aramid fibers,polypropylene fibers, polyethylene fibers, polyester fibers, vinylonfibers, polyimide fibers and polyimideamide fibers; metal fibers such astungsten fibers, molybdenum fibers, steel fibers and gallium fibers; andvarious products formed of such fibers or fiber products. Among these,glass fibers are preferred.

The thermosetting molding composition according to the present inventioncan contain, as needed, one or more of known auxiliary raw materials formolding materials, such as curing agents, fillers, mold release agents,colorants, stabilizers and preform bonding materials. In addition, aviscosity regulating agent such as a solvent can also be incorporated asneeded.

The thermosetting molding composition according to the present inventioncan provide a molded product in the presence or absence of a curingagent. A suitable curing agent can be chosen as needed.

Examples of the curing agent include, but are not limited to, mineralacids such as hydrochloric acid, sulfuric acid, phosphoric acid andnitric acid; carboxylic acids such as formic acid, benzoic acid,phthalic acid, acetic acid, α-chloroacetic acid, trifluoroacetic acid,propionic acid, salicylic acid, oxalic acid, lactic acid and aminoacids; sulfonic acids such as benzenesulfonic acid, p-toluenesulfonicacid and dodecylbenzenesulfonic acid; ammonium salts such as ammoniumchloride, ammonium sulfate, ammonium phosphate, ammoniumdihydrogenphosphate, diammonium hydrogenphosphate, ammonium nitrate,ammonium formate, ammonium acetate, ammonium p-toluenesulfonate,ammonium sulfamate and diammonium imidosulfonate; chloroacetamides; andwater-soluble metal salts of metals such as zinc, magnesium, calcium andaluminum with acids such as nitric acid, sulfuric acid and phosphoricacid, with ammonium salts such as ammonium nitrate and water-solublemetal salts such as zinc nitrate being preferred.

Usable exemplary fillers include, but are not limited to, calciumcarbonate, calcium sulfate, barium sulfate, hydrated alumina, calciumoxide, magnesium oxide, calcium hydroxide, magnesium hydroxide,ultrafine silica powder, mica, asbestos, clay, talc, silica sand, glassballoons, shirasu (white volcanic ash) balloons, sand, gravel, porcelainpowder, glass powder, polycarbonate powder, polyethylene powder, pulpdust, paper, waste threads and fabric pieces.

Illustrative examples of the mold release agent include, but are notlimited to, wax, POVAL (polyvinyl alcohol), silicone, zinc stearate,magnesium stearate, calcium stearate, aluminum distearate, stearic acid,soybean lecithin, carboxylic esters such as dimethyl oxalate, maleicanhydride, phthalic anhydride, and organophosphoric esters. These moldrelease agents can be chosen freely as needed depending on the moldingmethod, the material and shape of the mold, the post-coating, etc.

In the thermosetting molding composition according to the presentinvention, a dye and/or a pigment can be used as a colorant to give adesired color to molded products or coatings.

Illustrative examples of the colorant include but are not limited to,cadmium red, red iron oxide, Lake Red G, Carmine 6B, condensed azo red,quinacridone red, perylenes, anthraquinone, cadmium orange, chromevermilion, pyrazolones, perinones, cadmium yellow, chrome yellow, yellowiron oxide, titanium yellow, disazo yellow, isoindolinones, chromiumoxide, copper phthalocyanine green, ultramarine, cobalt blue, copperphthalocyanine blue, quinacridone violet, dioxadiviolet, titanium white,black iron oxide, carbon black, Oil Orange S, Rhodamine B, and Rhodamine6GCP.

Upon production, processing or forming of the thermosetting moldingcomposition according to the present invention, known methods which areemployed for molding compositions are all useful and can be chosen foruse as needed. For example, materials which are generally used inmolding materials are added at a desired stage until the amino resinreaches the B-stage. The resulting mass is thoroughly kneaded at roomtemperature or under heat by using a kneader, a heating roll, anextruder or the like. A curing agent, a mold release agent, a colorantand/or the like are then added as needed, followed by grinding in a ballmill or the like. As another example, a glass cloth or the like isimpregnated with a liquid formulation of the amino resin, followed bydesolvation or the like. The glass cloth of the like so treated is thensubjected to aging under heat. As a further example, a mixture--whichhas been formed by uniformly dispersing a curing agent, a filler, a moldrelease agent, a colorant and/or the like in a liquid formulation of theamino resin--is coated on a film of polyethylene or the like. Thethus-coated film is then compression-bonded to a desired reinforcingmaterial such as glass fibers to impregnate the reinforcing materialwith the mixture, whereby a sheet-like prepreg is obtained. This prepregis subjected to defoaming, desolvation and the like, followed by aging.As a still further example, a liquid formulation of the amino resin isadded with a curing agent, a filler, a mold release agent, a colorantand/or the like, followed by desolvation. The resulting mixture iskneaded in a kneader, to which glass fibers are added and then dispersedevenly. The mass so molded is then taken out of the kneader, dividedinto desired sizes and then subjected to aging. It is however borne inmind that the production, processing and/or molding of the thermosettingmolding composition is not limited to the methods exemplified above.

In the thermosetting molding composition according to the presentinvention, the reinforcing material is preferably glass fibers.

It is more preferred to incorporate at least one of the curing agents.

The above-described thermosetting molding composition according to thepresent invention can preferably be used as a laminate-moldingcomposition, a sheet molding composition or a bulk molding composition.

As has been described above, the thermosetting molding compositionaccording to the present invention can be added with various componentsas needed. These components can be changed in various ways depending onthe workability, the molding conditions, the application of the moldedproduct and the like. Preferred compositions may comprise, for example,5-95 parts by weight of an amino resin useful in the present invention,0.5-10 parts by weight of a curing agent, 0-90 parts by weight of afiller, 5-90 parts by weight of a reinforcing material and 0-50 parts byweight of a mold release agent, although the thermosetting moldingcomposition according to the present invention is not limited to them.

The thermosetting molding composition according to this invention, whichhas been obtained as described above, has excellent flowability uponmolding, so that it can be employed for the formation of products havingcomplex shapes or large dimensions. Molded products, which have beenobtained using the thermosetting molding composition, are excellent inweatherability, heat resistance, flame retardancy, electricalcharacteristics, mechanical properties and the like and are useful in awide variety of fields, for example, household appliances such as bathtabs, purifying tanks, sink cabinets, table ware and chairs; automobileparts and components such as fenders, front and rear skirts, enginehoods, wheel caps and instrument panels; corrosion-resistant equipmentssuch as filter presses, pump housings, tanks, vessels and cleaningtowers; mechanical parts and components; and electrical parts andcomponents such as switch boxes, meters, covers, electrically insulatingparts, laminated substrates and electronic circuit boards.

This invention also provides an excellent thermosettingexpansion-forming composition which makes use of an amino resin obtainedfrom one or more of the above-described diguanamines and diguanaminederivatives.

The proportion of the diguanamine or the diguanamine derivative in thethermosetting expansion-forming composition according to the presentinvention can be chosen freely depending on the desired properties. Toprovide a thermosetting expansion-forming composition which hasexcellent solubility or dispersibility in a solvent such as water andsuperb storage stability and can provide foams excellent in heatinsulating property, soundproofing property, flame retardancy,mechanical properties and the like, it is preferred to control theproportion of the diguanamine or the diguanamine derivative in an amountof at least 40 wt. %, more desirably at last 80 wt. % based on the aminocompound.

To obtain a liquid amino resin formulation, which has better stabilityin an aqueous solution and can provide foams superior in mechanicalproperties such as elongation at break, by using the diguanaminederivative, the diguanamine derivative should amount preferably to0.1-80 wt. %, more preferably 1-60 wt. % based on the amino compound.

The amino compound useful in the present invention can include one ormore compounds other than the above-described diguanamines anddiguanamine derivatives, for example, one or more of the amino compoundsexemplified above in connection with the thermosetting moldingcomposition to an extent not impairing the significance of the use ofthe amino compound in the present invention, so that these compoundsshould amount preferably to less than 60% based on the amino compound.

As the aldehyde in the thermosetting expansion-forming compositionaccording to the present invention, aldehydes usable, for example, inthe above-described thermosetting molding composition are also useful.Among these, formaldehydes and glyoxal are preferred, with an aqueoussolution of formaldehyde and paraformaldehyde being more preferred. Suchformaldehyde(s) preferably account for at least 50 wt. % of thealdehyde. The aldehyde can be used generally in an amount of 1.0-16moles, preferably 1.5-8.0 moles, more preferably 2.5-6.0 moles per moleof the amino compound.

Although no particular limitation is imposed on the manner of obtainingthe amino resin for use in the production of the thermosettingexpansion-forming composition according to the present invention,several processes may be mentioned as examples. A liquid mixture, whichhas been formed by stirring and mixing the above-described aminocompound and aldehyde in one or more solvents such as water, alcoholsand/or aromatic compounds, is subjected to an addition reaction at 30°-80° C. and pH 8-13, whereby an N-methyloldiguanamine is obtained. As analternative, such a liquid mixture is subjected to addition condensationunder high alkaline conditions of pH 13 or higher or under conditions ofpH 8 or lower, whereby a primary condensate of the N-methyloldiguanamineis obtained. As a further alternative, the N-methyloldiguanamine or theprimary condensate of the N-methyloldiguanamine so obtained is caused toundergo further condensation at pH 1-6 and 30°-80° C. so that acondensate is obtained with an increased condensation degree.

When an amino resin useful in the present invention is produced usingthe diguanamine or diguanamine derivative in a manner described above,the amino resin shows good water solubility even when its methylolationis allowed to proceed to a high degree. The amino resin so obtained isexcellent in solubility, dispersibility, storage stability and the likeand, moreover, has the excellent characteristic that no precipitation isobserved even when the reaction is carried out at a high concentration.The resulting amino resin also has the excellent feature that itcontains neither much low-molecular substances as sources for theformation of a precipitate, said low-molecular substances beingresponsible for reduced mechanical properties of a foam to be obtained,nor much high-molecular substances and branched substances as causes forpoor solubility and/or dispersibility. The amino resin so obtained issuperior to that available when the hydroxyl-containing diguanaminederivative is used. Use of such an amino resin can provide athermosetting expansion-forming composition which is excellent insolubility, dispersibility, storage stability, production readiness andthe like and can afford foams having excellent mechanical properties andthe like.

A modified amino resin can be obtained by sulfonating a product whichhas been obtained by reacting an amino compound, which contains theabove-described diguanamine or diguanamine derivative, with an aldehyde.This modified amino resin is also extremely useful as a component inthermosetting expansion-forming composition according to the presentinvention.

The modified amino resin can be obtained by adjusting the pH of anaqueous solution of the above-described N-methyloldiguanamine or primarycondensate of N-methyloldiguanamine to 10-13, adding a sulfonating agentsuch as an alkali sulfite to the aqueous solution and then stirring theresultant mixture at 60°-80° C. until no sulfite salt is detected.

Also useful is a resin obtained by subjecting the modified product tocondensation at pH 1.0-6.0 and 30°-80° C. to increase its condensationdegree by an appropriate degree. The sulfonating agent can be usedgenerally in an amount of 0.05-3.0 moles, preferably 0.1-2.0 moles permole of the amino compound.

The modified amino resin has still better solubility or dispersibilityin a solvent such as water, so that good solubility or dispersibilitycan be retained even if its condensation degree is increasedsubstantially compared with the corresponding unmodified amino resin.Use of such a modified amino resin makes it possible to provide anexpansion-forming composition excellent in storage stability,emulsifiability and the like and also a foam excellent in mechanicalproperties and the like.

Also useful is that obtained by heating an amino resin or modified aminoresin, which has been obtained by conducting a reaction as describedabove, to 60°-150° C. under normal pressure or reduced pressure so thatwater originated from an aldehyde as a raw material, water formed by acondensation reaction, a solvent or the like are eliminated. It ishowever to be noted that the manner of production of the amino resin isnot limited to the processes described above and conventionally knownprocesses can also be used likewise. In some instances, it is possibleto choose conditions such as the condensation degree, methylolationdegree and/or sulfonation degree of the amino resin or modified aminoresin, the solvent, pH, etc. as needed.

Such an emulsifier can lower the interfacial tension between the aminoresin or modified amino resin, the foaming agent and the solvent such aswater, so that the system so formed can be uniformly emulsified ordispersed into a stable system. Upon production of a foam, theemulsifier acts on minute bubbles so that the bubbles can be rendereduniform and stable. Use of the emulsifier is therefore preferred forobtaining a desired foam.

Illustrative emulsifiers include, but are not limited to, anionicemulsifiers, for example, alkylbenzenesulfonates such as sodiumdodecylbenzenesulfonate and sodium dodecyldiphenylether disulfonate,alkyl naphthatenesulfonates such as sodium dipropylnaphthalenesulfonateand sodium naphthalenesulfonateformaldehyde condensate, alkylsulfonatessuch as sodium octadecanesulfonate and potassium dodecanesulfonatedialkylsulfosuccinates such as sodium diisobutylsulfosuccinate andsodium dioctylsulfosuccinate, α-sulfonated fatty acid salts such assodium α-sulfopalmitate, N-methyltaurine salts such as sodiumN-methyl-N-oleyltaurine, sulfated oils such as α-olefinsulfonates,petroleum sulfonates and turkey red oil, alkylsulfates such as sodiumlaurylsulfate, sulfate esters such as polyoxyethylene alkyl ether,polyoxyethylene alkylphenyl ether, phosphate esters and salts, andalkylphosphate salts; nonionic emulsifiers, for example, the ethyleneoxide adducts of alcohols, carboxylic acids and phenols, such aspolyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether andsorbitol tristearate, and block copolymers such as ethyleneoxide-propylene oxide block copolymers; cationic emulsifiers such aslaurylamine acetate, stearyl trimethyl ammonium chloride, stearyl benzyldimethyl ammonium chloride and dodecylpyridium bromide; and amphotericemulsifiers such as lauryl betaine and stearyl betaine, with anionicemulsifiers and non-ionic emulsifiers being preferred. The emulsifiercan be used in an amount of 0.2-5.0 wt. %, preferably 0.5-4.0 wt. %based on the total amount of the above-described amino resin and/ormodified amino resin.

As such a foaming agent, it is possible to incorporate water or analcohol as a solvent or a dispersant in a thermosetting moldingcomposition according to the present invention and to use it as aprincipal component of the foaming agent. It is however preferred toincorporate a volatile foaming agent having a boiling point in a rangeof from -20° C. to 100° C., preferably from 20° C. to 80° C.Illustrative examples of the volatile foaming agent include, but are notlimited to, aliphatic, alicyclic and aromatic hydrocarbons, halogenatedhydrocarbons, alcohols, ketones, ethers, esters, azo compounds,carbonates and isocyanates, with pentane, hexane, heptane,trichlorotrifluoroethane, trichlorofluoromethane and the like beingpreferred. The amount of the volatile foaming agent can be chosen freelyas needed depending on the desired final density of the foam and thekind of the foaming agent. In generally, the volatile foaming agent isused in an amount of 1-50 wt. %, preferably 3-40 wt. % based on thetotal amount of the above-described amino resin and/or modified aminoresin.

As the curing agent, any compound can be used as long as it can releaseor form protons under production conditions. Compounds having high watersolubility are preferred. For example, the curing agents usable in theabove-described thermosetting molding composition are also useful.Formaldehyde itself forms formic acid and acts as a curing agent, sothat formaldehyde is also useful. It is however to be noted that thecuring agent is not limited to such exemplified ones. The curing agentcan be used in an amount of 0.01-20 wt. %, preferably 0.05-5 wt. % basedon the total amount of the above-described amino resin and/or modifiedamino resin.

Further, the thermosetting expansion-forming composition according tothe present invention can contain other additives, for example, a dye orpigment, a flame retardant and/or a filler, a reinforcing material suchas glass fibers, carbon fibers or polyaramid fibers, a gas toxicitylowering agent, a hydrophobicity imparting agent, a mold release agent,a mildewproofing agent, a bacteriocide and/or one or more other polymersas needed insofar as the effects of the present invention are notimpaired.

In the thermosetting expansion-forming composition according to thepresent invention, the concentration of the above-described amino resinand/or modified amino resin in a solvent such as water is chosen asdesired depending on the temperature of a system in which foaming isconducted, the kind of the foaming agent, the viscosity of the liquidformulation at the time of initiation of foaming, etc. In general, theconcentration is in a range of from 50 wt. % to 90 wt. %, preferably ina range of from 60 wt. % to 85 wt. %.

No particular limitation is imposed on the manner of production of anelastic foam according to the present invention. Processes which areemployed upon foaming known expansion-forming liquid resin formulationscan be applied. For example, the above-described thermosettingexpansion-forming composition is supported on a heating band or the likeand is heated by radiation such as hypersonic wave (0.2 GHz to 100 GHz),infrared rays or far infrared rays, hot air or the like to a temperaturesufficient to cause evaporation or boiling of the foaming agent orproduction of blowing gas such as carbon dioxide under a preset pressurewhile choosing the quantities of radiation, heat and the like, wherebyits foaming and curing are conducted. It is however borne in mind thatthe production process is not limited to the above-exemplified one.

It is also useful to subject the thus-obtained elastic foam topost-treatment, for example, to heat the elastic foam at 100°-250° C.for 1-200 minutes to sufficiently eliminate a solvent such as water, afoaming agent, formaldehyde and the like and then to cure thethus-heated elastic foam or to compress the elastic foam by 40-90% andthen to allow it to expand. Such post-treatment has excellent effectssuch that the resulting elastic foam has a smaller shrinkage factor, alower equilibrium moisture content and an improved modulus of elasticityand the release of formaldehyde from the resulting elastic foam issubstantially reduced.

The elastic foam so obtained can be used as is or after cutting it intoa desired plate, sheet or the like. As a further alternative, a coverlayer can be applied or bonded to one or each side of the elastic foamby using a paper sheet, a cardboard, a board, a gypsum board, a metalplate, a metal foil, a plastic sheet or the like.

The thermosetting expansion-forming composition according to the presentinvention is excellent in heat insulating property, sound absorbingqualities, heat resistance, flame retardancy, impact resistance,vibration resistance and the like and can provide foams useful for awide variety of applications, for example, as heat-insulating soundproofmaterials such as dividing walls (partitions), wall materials, ceilingmaterials, door materials, floor materials, curtain wall core materialsand panel core materials for buildings; low-temperature heat insulatingmaterials for roofs, eaves and the like of refrigerators, freezers,liquefied gas containers, containers and cold storages; low-temperatureinsulating materials for oil and like storage tanks, ducts, pipes andthe like in factories; flame-retardant fillers for metal sidings,sealing materials and heat-resistant materials; heat-insulatingsoundproof materials, vibration-resistant materials and cushioningmaterials for transportation equipments such as automobiles, vehiclesand aircraft; impact-absorbing packing materials; fillers; and the like.

In the above-described thermosetting expansion-forming composition, theemulsifier is preferably at least one emulsifier selected from anionicemulsifiers and nonionic emulsifiers while the foaming agent ispreferably a volatile foaming agent having a boiling point in a range of20°-80° C. under normal pressure.

Further, a particularly useful elastic foam is one having a bulk densityof 1.5-80 g/l and obtained by foaming and curing a liquid formulation ofthe above-described thermosetting expansion-forming composition.

Owing to the use of the amino resin obtained by reacting the aminocompound, which contains the novel diguanamine having the particularstructure, with the aldehyde, the above-described thermosetting moldingcomposition according to the present invention features simple and easyproduction and handling of the resin and composition, shows excellentformability and flowability upon molding, permits easy forming ofproduct of complex shapes and can provide formed products excellent inhigh-temperature discoloration resistance, light resistance, electricalcharacteristics such as electrical insulating property and arcresistance, heat resistance, flame retardancy, mechanical properties andthe like. The thermosetting molding composition is useful as a generalmolding material, a laminate-molding material, a sheet molding material,a bulk molding material or the like and its application can be expandedto a wide variety of fields such as household appliances, parts andcomponents of transportation equipments such as automobiles, industrialparts and components, tanks, containers, apparatuses, and electricalparts and components such as electrical insulating materials andelectronic circuit substrates. This invention is therefore extremelyimportant from the industrial standpoint.

Owing to the use of the amino resin obtained by reacting the aminocompound, which contains the novel diguanamine having the particularstructure, with the aldehyde, and/or the modified amino resin obtainedby sulfonating the amino resin, the thermosetting expansion-formingcomposition according to the present invention has extremely goodsolubility or dispersibility in a solvent such as water and alsoextremely good storage stability, features simple and easy production ofthe resin and the composition, provides excellent foams and are henceextremely useful. By foaming and curing the thermosettingexpansion-forming composition, it is possible to provide an elastic foamexcellent in heat insulating property, soundproofing qualities, flameretardancy, heat resistance, impact resistance, vibration resistance,processability, formability, mechanical properties and the like. Thethermosetting expansion-forming composition is therefore extremelyuseful for a wide variety of applications, for example, asheat-insulating materials and sound-deadening and soundproof materialsfor dividing walls (partitions), roofs, doors and floors of buildingsand the like, refrigerators, constant-temperature rooms and the like;heat-insulating materials, soundproof materials and heat insulatingbarriers for transportation equipments such as automobiles, vehicles andaircraft; heat insulating materials for tanks, containers and the likein industrial equipments; insulating materials; impact absorbingpackaging materials; fillers; etc. The present invention is thereforeextremely important from the industrial standpoint.

The present invention will next be described in detail by the followingreferential examples and examples. It should however be borne in mindthat this invention is by no means limited to or by these referentialexamples and examples.

Incidentally, tests of the elastic foam in each Example were performedin accordance with the following testing methods:

(1) bulk density (g/l)--DIN 53420,

(2) percent shape restoration (%)--DIN 53577,

(3) deformation at break (mm)--DIN 53423,

(4) tensile strength (N/mm²)--DIN 53571, and

(5) fire resistance--DIN 4102.

REFERENTIAL EXAMPLE 1 Preparation of a Dicarbonitrile (3)

In a 500 ml flask equipped with a stirrer, a thermometer, a liquid inlettube and a condenser, 297.92 g (2.50 moles) ofbicyclo[2.2.1]hepta-5-ene-2-carbonitrile, 8.77 g (6.75 mmoles) ofNi[P(OC₆ H₅)₃ ]₄, 4.80 g (35.22 mmoles) of ZnCl₂ and 32.27 g (0.104mole) of P(OC₆ H₅)₃ were charged. After the flask was fully purged withnitrogen gas, the reaction mixture was maintained at 65° C. understirring. Into the flask, 94.59 g (3.50 moles) of ice-cooled liquidhydrocyanic acid were then charged at a flow rate of 45-55 ml/hr overthree hours, followed by a further reaction for one hour.

The flask was again purged with nitrogen gas, followed by the additionof deionized water. The water layer so obtained was removed, whereby anoil was obtained in a semi-solid form. The oil was filtered and then wassubjected to vacuum distillation, whereby 362.20 g of a mixture ofbicyclo[2.2.1]heptane-2,5-dicarbonitrile andbicyclo[2.2.1]heptane-2,6-dicarbonitrile were obtained at 129°-137° C./1mmHg (yield: 99.01%). The following is the results of an elementalanalysis of the target product.

    ______________________________________                                        Elemental analysis:                                                                    C          H       N                                                 ______________________________________                                        Found:     73.9%        6.9%    19.2%                                         Calculated:                                                                              73.94%       6.90%   19.16%                                        ______________________________________                                    

REFERENTIAL EXAMPLE 2 Preparation ofBicyclo[2.2.1]Heptane-2,5-Dicarbonitrile

In a 2 l flask equipped with a stirrer, a thermometer and a refluxcondenser, 179.0 g (1.2 moles) of5-cyano-bicyclo[2.2.1]hepta-2-carbaldehyde, 292.6 g (1.3 moles) ofN,O-bis(trifluoroacetyl)hydroxylamine, 197.8 g (2.5 moles) of pyridineand 600 ml of benzene were charged. The resulting mixture was graduallyheated and refluxed for 3 hours under stirring. Deionized water (500 ml)was thereafter added to the reaction mixture. The water layer soobtained was removed, whereby an oil was obtained. The oil was distilledunder reduced pressure, whereby 128.0 g ofbicyclo[2.2.1]heptane-2,5-dicarbonitrile were obtained at 131°-136° C./1mmHg (yield: 73%). The following is the results of an elemental analysisof the target product.

    ______________________________________                                        Elemental analysis:                                                                    C          H       N                                                 ______________________________________                                        Found:     74.0%        6.9%    19.1%                                         Calculated:                                                                              73.94%       6.90%   19.16%                                        ______________________________________                                    

REFERENTIAL EXAMPLE 3 Preparation of a Dicarbonitrile (4)

In a 500 ml flask equipped with a stirrer, a thermometer, a gas inlettube and a condenser, 188.6 g of 4-cyanocyclohexene, 6.0 g of Ni[P(OC₆H₅)₃ ]₄, 3.0 g of ZnCl₂ and 23.9 g of P(OC₆ H₅)₃ were charged. After theflask was fully purged with nitrogen gas, the reaction mixture wasmaintained at 75° C. under stirring. Into the flask, nitrogen-dilutedhydrocyanic acid gas having a concentration of 42 mole % was thencharged at a rate of 177.0 mmoles/hour for seven hours. After the flaskwas again purged with nitrogen gas, the reaction mixture was cooled. Asa result of its analysis, a dicarbonitrile (4) was obtained in a yieldof 64.9%.

Water and ethyl acetate, each 500 g, were added to the reaction mixture.After the resulting mixture was left over under stirring for 5 hours,the organic layer was separated. Ethyl acetate was then caused toevaporate, followed by vacuum distillation at 0.5-1.0 mmHg, whereby132.0 g of a mixture of 1,3-cyclohexane dicarbonitrile and1,4-cyclohexane dicarbonitrile were obtained as a 120°-130° C. fraction.As a result of its analysis, the fraction was found to consist of 64.4%of 1,3-cyclohexane dicarbonitrile and 35.6% of 1,4-cyclohexanedicarbonitrile. The following is the results of an elemental analysis ofthe target product.

    ______________________________________                                        Elemental analysis:                                                                    C          H       N                                                 ______________________________________                                        Found:     71.5%        7.6%    20.9%                                         Calculated:                                                                              71.61%       7.51%   20.88%                                        ______________________________________                                    

EXAMPLE 1 Preparation of a Diguanamine (1)

In a 3 l flask equipped with a stirrer, a thermometer and a refluxcondenser, 146.2 g (1.0 mole) of the dicarbonitrile (3) prepared in thesame manner as in Referential Example 1, 210.2 g (2.5 moles) ofdicyandiamide, 16.8 g of potassium hydroxide and 1,000 ml of methylcellosolve were charged, followed by gradual heating. The reactionmixture became transparent as its temperature arose. When thetemperature approached about 105° C., the reaction proceeded rapidlywith substantial exotherm so that the solvent was refluxed. Some timeafter the reflux started, the reaction mixture became turbid. Theresulting mixture was reacted at 120°-125° C. for 10 hours understirring. Subsequent to removal of the solvent from the reactionmixture, 3 l of deionized water were poured. The resulting whiteprecipitate was collected by filtration. The solid so obtained waswashed with deionized water and then with methanol, followed by vacuumdrying. The resulting solid was dissolved in ethyl cellosolve, to whichdeionized water was added to conduct precipitation. The precipitate wascollected by filtration. The solid so obtained was washed with water andthen dried in a vacuum, whereby2,5-bis(4,6-diamino-1,3,5-triazin-2-yl)-bicyclo[2.2.1]heptane and2,5-bis(-4,6-diamino-1,3,5-triazin-2-yl)bicyclo[2.2.1]-heptane wereobtained as mixture in the form of white powdery crystals having amelting point of 317°-324° C. (as measured by DSC). Incidentally, as aresult of an analysis of the reaction mixture (before treatment) byliquid chromatography, it was found that, based on the amount of thedicarbonitrile (3) charged, the yield (mole %) of the diguanamine (1)was 98.2% and that of compounds other than the raw materials and thetarget compound was 0.08 wt. %. The results of an elemental analysis and¹ H nuclear magnetic resonance spectrum analysis of the target compoundare presented below. In addition, the results of an infrared rayabsorption spectrum analysis and mass spectrum analysis of the targetcompound are shown in FIG. 1 and FIG. 2, respectively.

    ______________________________________                                        Elemental analysis:                                                                    C          H       N                                                 ______________________________________                                        Found:     49.7%        5.8%    44.5%                                         Calculated:                                                                              49.67%       5.77%   44.56%                                        ______________________________________                                    

¹ H Nuclear magnetic resonance spectrum analysis (internal standardsubstance: TMS, solvent: d₆ -DMSO)

Absorption based on NH₂ groups, δ6.50 ppm (singlet), 6.72 ppm (singlet)

EXAMPLE 2 Preparation of2,5-bis(4,6-diamino-1,3,5-triazin-2-yl)-bicyclo[2.2.1]heptane

In a similar manner to Example 1 except that 146.2 g (1.0 mole) of thedicarbonitrile (3) prepared in the same manner as in Referential Example1 were replaced by 160.8 g (1.1 moles) ofbicyclo[2.2.1]heptane-2,5-dicarbonitrile prepared in the same manner asin Referential Example 2, a reaction was conducted and the resultingreaction mixture was treated. The solid so obtained was subjected tovacuum drying, whereby2,5-bis(4,6-diamino-1,3,5-triazin-2-yl)-bicyclo[2.2.1]-heptane wasobtained as white powdery crystals having a melting point of 318°-321°C. (as measured by DSC). Incidentally, as a result of an analysis of thereaction mixture (before treatment) by liquid chromatography, it wasfound that the yield of the diguanamine (1) was 96.4 mole % based on theamount of the dicarbonitrile (3) charged. In an infrared absorptionspectrum of the target compound, the nitrile-based absorption (at 2235cm⁻¹) of the raw material compound disappeared and instead, atriazine-ring-based absorption was observed at 821 cm⁻¹. Its elementalanalysis data were found to conform well with the calculated values asshown below.

    ______________________________________                                        Elemental analysis:                                                                    C          H       N                                                 ______________________________________                                        Found:     49.7%        5.7%    44.6%                                         Calculated:                                                                              49.67%       5.77%   44.56%                                        ______________________________________                                    

EXAMPLE 3 Preparation of a Diguanamine (2)

In a 3 l flask equipped with a stirrer, a thermometer and a refluxcondenser, 134.2 g (1.0 mole) of the dicarbonitrile (4) prepared in thesame manner as in Referential Example 3, 210.2 g (2.5 moles) ofdicyandiamide, 16.8 g of potassium hydroxide and 1,000 ml of methylcellosolve were charged, followed by gradual heating. The reactionmixture became transparent as its temperature arose. When thetemperature approached about 105° C., the reaction proceeded rapidlywith substantial exotherm so that the solvent was refluxed. Some timeafter the reflux started, the reaction mixture became turbid. Theresulting mixture was reacted at 120-125° C. for 10 hours understirring.

Subsequent to the removal of the solvent from the reaction mixture, 3 lof deionized water were poured. The resulting white precipitate wascollected by filtration. The solid so obtained was washed with deionizedwater and then with methanol, followed by vacuum drying. The resultingsolid was dissolved in ethyl cellosolve, to which deionized water wasadded to induce reprecipitation. The precipitate so formed was collectedby filtration. The solid so obtained was washed with water and thendried in a vacuum, whereby1,3-bis(4,6-diamino-1,3,5-triazin-2-yl)-cyclohexane and1,4-bis(4,6-diamino-1,3,5-triazin-2-yl)cyclohexane were obtained as amixture in the form of white powdery crystals having a melting point of317°-321° C. (as measured by DSC). Incidentally, as a result of ananalysis of the reaction mixture (before treatment) by liquidchromatography, it was found that, based on the amount of thedicarbonitrile (4) charged the yield of the diguanamine (2) was 97.3mole % and that of the compound(s) except the raw materials and thetarget compound was 0.12 wt. %. The results of an elemental analysis and¹ H nuclear magnetic resonance spectrum analysis of the target compoundare presented below. In addition, the results of an infrared rayabsorption spectrum analysis and a mass spectrum analysis of the targetcompound are shown in FIG. 3 and FIG. 4, respectively.

    ______________________________________                                        Elemental analysis:                                                                    C          H       N                                                 ______________________________________                                        Found:     47.6%        6.1%    46.3%                                         Calculated:                                                                              47.67%       6.00%   46.33%                                        ______________________________________                                    

¹ H Nuclear magnetic resonance spectrum analysis (internal standardsubstance: TMS, solvent: d₆ -DMSO)

Absorption based on NH₂ groups, δ: 6.49 ppm (singlet)

EXAMPLE 4 Preparation of1,4-bis(4,6-diamino-1,3,5-triazin-2-yl)-cyclohexane

In a similar manner to Example 3 except that 134.2 g (1.0 mole) of thedicarbonitrile (4) prepared in the same manner as in Referential Example3 were replaced by 147.6 g (1.1 moles) of 1,4-cyclohexanedicarbonitrile, a reaction was conducted and the resulting reactionmixture was treated. The solid so obtained was subjected to vacuumdrying, whereby 1,4-bis(4,6-diamino-1,3,5-triazin-2-yl)-cyclohexane wasobtained as white powdery crystals having a melting point of 319°-322°C. (as measured by DSC). Incidentally, as a result of an analysis of thereaction mixture (before treatment) by liquid chromatography, it wasfound that, based on the amount of the dicarbonitrile (4) charged, theyield of the diguanamine (2) was 95.8 mole %. In an infrared absorptionspectrum of the target compound, it was found that the nitrile-basedabsorption (at 2237 cm⁻¹) of the raw material compound disappeared andinstead, a triazine-ring-based absorption was newly observed at 821cm⁻¹. Its elemental analysis data were found to conform well with thecalculated values as shown below.

    ______________________________________                                        Elemental analysis:                                                                    C          H       N                                                 ______________________________________                                        Found:     47.7%        6.1%    46.2%                                         Calculated:                                                                              47.67%       6.00%   46.33%                                        ______________________________________                                    

¹ H Nuclear magnetic resonance spectrum (internal standard substance:TMS, solvent: d₆ -DMSO)

Absorption based on NH₂ groups δ: 6.50 ppm (singlet)

EXAMPLE 5 Preparation of1,2-bis(4,6-diamino-1,3,5-triazin-2-yl)-cyclohexane

In a similar manner to Example 3 except that 134.2 g (1.0 mole) of thedicarbonitrile (4) prepared in the same manner as in Referential Example3 were replaced by 134.2 g (1.0 mole) of 1.2-cyclohexane dicarbonitrile,a reaction was conducted and the resulting reaction mixture was treated.The solid so obtained was subjected to vacuum drying, whereby1,2-bis(4,6-diamino-1,3,5-triazin-2-yl)-cyclohexane was obtained aswhite powdery crystals. In an infrared absorption spectrum of the targetcompound, the nitrile-based absorption of the raw material compounddisappeared and instead, a triazine-ring based absorption was newlyobserved. Its elemental analysis data were found to conform well withthe calculated value as shown below

    ______________________________________                                        Elemental analysis:                                                                    C          H       N                                                 ______________________________________                                        Found:     47.7%        6.0%    46.3%                                         Calculated:                                                                              47.67%       6.00%   46.33%                                        ______________________________________                                    

EXAMPLE 6 Preparation of Diguanamines (1)

In a similar manner to Example 1 except that the charged amount (inmoles) of dicyandiamide and the reaction solvent were changed, reactionswere conducted and the reaction mixtures so obtained were treated. Theyields of the target compounds, diguanamines (1), are shown in Table 1.

                  TABLE 1                                                         ______________________________________                                                                   Yield* of di-                                                                 guanamine (1)                                      Amount of                  [based on dicar-                                   dicyandiamide   Reaction   bonitrile (3)                                      charged (moles) solvent    charged (mole %)]                                  ______________________________________                                        Example 2.2         Ethyl      95.8                                           6-1                 cellosolve                                                Example 2.5         Ethylene   97.0                                           6-2                 glycol                                                    Example 2.5         A mixed    98.2                                           6-3                 solvent of                                                                    dimethyl                                                                      sulfoxide/                                                                    methyl                                                                        cellosolve                                                                    (weight                                                                       ratio: 1/1)                                               ______________________________________                                         *Calculated based on the results of liquid chromatography of each reactio     mixture (before treatment)                                               

EXAMPLE 7 Preparation of a Diguanamine (1)

In a 3 l flask equipped with a stirrer, a thermometer and a refluxcondenser, 146.2 g (1.0 mole) of the dicarbonitrile (3) obtained in thesame manner as in Referential Example 1, 210.2 g (2.5 moles) ofdicyandiamide, 54.0 g of sodium methylate and 1,000 ml of dimethylsulfoxide were charged, followed by gradual heating. When thetemperature approached about 105° C., the reaction proceeded rapidlywith substantial exotherm. The temperature was thereafter raisedgradually to 140° C., followed by reaction at 140°-145° C. for 2 hoursunder stirring.

The reaction mixture so obtained was treated in a similar manner toExample 1, whereby2,5-bis(4,6-diamino-1,3,5-triazin-2-yl)-bicyclo[2.2.1]heptane and2,6-bis(4,6-diamino-1,3,5-triazin-2-yl)-bicyclo[2.2.1]-heptane wasobtained as a mixture. Incidentally, as a result of an analysis of thereaction mixture (before treatment) by liquid chromatography, it wasfound that, based on the amount of the dicarbonitrile (3) charged, theyield of the diguanamine (1) was 99.7 mole %.

EXAMPLE 8 Preparation of Diguanamines (2)

In a similar manner to Example 3 except that the charged amount (inmoles) of dicyandiamide and the reaction solvent were changed, reactionswere conducted and the reaction mixtures so obtained were treated. Theyields of the target compounds, diguanamines (2), are shown in Table 2.

                  TABLE 2                                                         ______________________________________                                                                   Yield** of di-                                                                guanamine (1)                                      Amount of                  [based on dicar-                                   dicyandiamide  Reaction    bonitrile (3)                                      charged (moles)                                                                              solvent     charged (mole %)]                                  ______________________________________                                        Example                                                                              2.5         Isopropyl   96.1                                           8-1                cellosolve                                                 Example                                                                              1.7         N,N-dimethyl-                                                                             61.5                                           8-2                acetamide                                                  Example                                                                              2.5         Sulforan    98.2                                           8-3                                                                           Example                                                                              3.0         A mixed     98.6                                           8-4                solvent of                                                                    dimethyl                                                                      sulfoxide/                                                                    methyl                                                                        cellosolve                                                                    (weight                                                                       ratio: 1/1)                                                ______________________________________                                         **Calculated based on the results of liquid chromatography of each            reaction mixture (before treatment)                                      

EXAMPLE 9 Preparation of 1,4-bis(4,6-diamino-1,3,5-triazin-2-yl)cyclohexane

In a 3 l flask equipped with a stirrer, a thermometer and a refluxcondenser, 134.2 g (1.0 mole) of 1,4-cyclohexane dicarbonitrile, 210.2 g(2.5 moles) of dicyandiamide, 54.0 g of sodium methylate and 1,000 ml ofdimethyl sulfoxide were charged, followed by gradual heating. Thereaction mixture became transparent as its temperature arose. When thetemperature approached about 105° C., the reaction proceeded rapidlywith substantial exotherm. The temperature was thereafter raised to 140°C., followed by reaction at 140°-145° C. for 2 hours under stirring.

The reaction mixture so obtained was treated in a similar manner toExample 3, whereby 1,4-bis(4,6-diamino-1,3,5-triazin-2-yl)-cyclohexanewas obtained as white powdery crystals. Incidentally, as a result of ananalysis of the reaction mixture (before treatment) by liquidchromatography, it was found that the yield of the diguanamine (2) was99.1 mole % based on the amount of the dicarbonitrile (4) charged.

According to the preparation process of the present invention which canprovide a diguanamine by reacting a particular dicarbonitrile anddicyandiamide while suitably selecting a reaction catalyst, a solvent, areaction temperature, the molar ratio of the raw materials and/or thelike, the target compound can be obtained with extremely minimizedbyproducts and high purity and in a high yield as demonstrated above inExamples 1-9. The process, including the purification step, is easy topractice and is excellent.

EXAMPLE 10 Preparation of an N-methylol Derivative of a Diguanamine (1)and Water Dilution Test of the Derivative

To 15.7 g (0.05 mole) of the diguanamine (1) obtained in the same manneras in Example 1, 42.2 g of 37% formalin (0.52 mole in terms of 100%formaldehyde) which had been adjusted to pH 10.5 with a 10% aqueoussolution of sodium hydroxide were added. The resulting mixture washeated at 60°-65° C. for 30 minutes under stirring. The reaction mixturewas homogeneous and clear. As a result of its analysis, it was foundthat 7.2 moles of formaldehyde were methylol-bonded to one mole of thediguanamine (1).

To the resulting solution of the N-methylol derivative, 50 g ofdeionized water were gradually added at room temperature. The solutionso obtained was also homogeneous and clear.

EXAMPLE 11 Preparation of an N-methylol Derivative of a Diguanamine (2)and a Water Dilution Test of the Derivative

To 15.1 g (0.05 mole) of the diguanamine (2) obtained in the same manneras in Example 3, 42.2 g of 37% formalin (0.52 mole in terms of 100%formaldehyde) which had been adjusted to pH 10.5 with a 10% aqueoussolution of sodium hydroxide were added. The resulting mixture washeated at 60°-65° C. for 30 minutes under stirring.

The reaction mixture was homogeneous and clear. As a result of itsanalysis, it was found that 7.3 moles of formaldehyde weremethylol-bonded to one mole of the diguanamine (2).

To the resulting solution of the N-methylol derivative, 50 g ofdeionized water were gradually added at room temperature. The solutionso obtained was also homogeneous and clear.

As demonstrated in Examples 10 and 11, the N-methylol derivative of eachdiguanamine according to the present invention has been found to haveexcellent water reducibility so that it is excellent as a raw materialfor a resin to be used in an aqueous system such as a water-base paintresin and is extremely useful for a wide variety of applications.

COMPARATIVE EXAMPLE 1 Preparation of an N-methylol Derivative ofPhthaloguanamine and a Water Dilution Test of the Derivative

In a similar manner to Example 10 except 14.8 g (0.05 mole) ofo-phthaloguanamine were used instead of 15.7 g (0.05 mole) of thediguanamine (1) obtained in the same manner as in Example 1, a reactionwas conducted.

The reaction mixture contained a large amount of an insoluble solid sothat it was subjected to solid-liquid separation by hot filtration. Thesolid was dried under reduced pressure, whereby 13.7 g of crystals,which were found to contain 13.6 g (0.046 mole) of o-phthaloguanamine asa result of an elemental analysis, were obtained. Deionized water (1.0g) was then added to the filtrate at room temperature, wherebysubstantial turbidity occurred.

COMPARATIVE EXAMPLE 2 Preparation of an N-methylol Derivative ofSpiroguanamine and a Water Dilution Test of the Derivative

In a similar manner to Example 10 except 15.7 g (0.05 mole) of thediguanamine (1) obtained in the same manner as in Example 1 werereplaced by 21.7 g (0.05 mole) of3,9-bis[2-(3,5-diamino-2,4,6-triazaphenyl)ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane]("CTU guanamine"; product of Ajinomoto Co., Inc.), a reaction wasconducted.

The reaction mixture so obtained contained a large amount of aninsoluble solid so that it was subjected to solid-liquid separation byhot filtration. The solid was dried under reduced pressure, whereby 18.3g of crystals, which were found to contain 18.2 g (0.042 mole) of CTUguanamine as a result of an elemental analysis, were obtained. Deionizedwater (1.0 g) was then added to the filtrate at room temperature,whereby substantial turbidity occurred.

As have been demonstrated above in Comparative Examples 1 and 2,methylol-forming reaction of phthaloguanamine and spiroguanamine withaldehydes are extremely slow. The amino groups in such compounds havepoor reactivity, so that it is difficult to produce resin intermediates,such as co-condensates with melamine, guanamines or ureas, or variousderivatives. Further, the N-methylol derivatives of such compounds haveextremely poor water reducibility. It is hence difficult to employ themas raw materials for resins to be used in aqueous systems, such aswater-base paint resins. Moreover, substantial limitations are imposedon their applications.

EXAMPLE 12 Preparation of an N-methylol Derivative of a Diguanamine (1)

To 15.7 g (0.05 mole) of the diguanamine (1) obtained in the same manneras in Example 1, 17.9 g of 37% formaldehyde (0.22 mole in terms of 100%formaldehyde) which had been adjusted to pH 9.0 with a 5% aqueoussolution of sodium carbonate were added. The resulting mixture washeated at 70°-75° C. for 30 minutes under stirring. The reaction mixturewas clear. As a result of an analysis of the mixture, it was found that4.0 moles of formaldehyde were methylol-bonded with one mole of thediguanamine (1).

EXAMPLE 13 Preparation of an N-methylol derivative of a Diguanamine (1)

To 15.7 g (0.05 mole) of the diguanamine (1) obtained in the same manneras in Example 1, 19.9 g (0.32 mole) of methylhemiformal and 40.0 g ofmethanol were added, followed by the adjustment to pH 9.5 with a 20%aqueous solution of potassium hydroxide. The resulting mixture washeated at 60° C. for one hour under stirring. The reaction mixture wasclear. As a result of an analysis of the mixture, it was found that 6.1moles of formaldehyde were methylol-bonded with one mole of thediguanamine (1).

EXAMPLE 14 Preparation of an N-methylol Derivative of a Diguanamine (1)

To 15.7 g (0.05 mole) of2,5-bis(4,6-diamino-1,3,5-triazin-2-yl)-bicyclo[2.2.1]heptane obtainedin the same manner as in Example 2, 81.2 g of 37% formalin (1.0 mole interms of 100% formaldehyde) which had been adjusted to pH 10.5 with a 5%aqueous solution of sodium hydroxide were added. The resulting mixturewas heated at 60° C. for one hour under stirring. The reaction mixturewas clear. As a result of an analysis of the mixture, it was found that7.8 moles of formaldehyde were methylol-bonded to one mole of2,5-bis(4,6-diamino-1,3,5-triazin-2-yl)-bicyclo[2.2.1]heptane.

EXAMPLE 15 Preparation of an N-methoxymethyl Derivative of a Diguanamine(1)

Under reduced pressure, the N-methylol derivative of 5.0 g of thediguanamine (1), said derivative being a reaction mixture prepared inthe same manner as in Example 10 and being formed of formaldehyde andthe diguanamine bonded together at a molar ratio of 7.2:1, wasdehydrated, followed by the addition of 50 ml of methanol. After beingadjusted to pH 2.0 with a 20% nitric acid, the resulting mixture washeated at 40°- 45° C. for 2 hours. The reaction mixture was adjusted topH 8.0 with a 10% aqueous solution of sodium hydroxide. From thesolution, methanol and water were removed under reduced pressure andthen a solid was then filtered off, whereby a viscous liquid wasobtained. As a result of an analysis of the liquid, it was found that5.3 equivalents of N-methoxymethyl groups were bonded to one mole of thediguanamine (1).

EXAMPLE 16 Preparation of an N-methoxymethyl Derivative of a Diguanamine(2)

Under reduced pressure, the N-methylol derivative of 5.0 g of thediguanamine (2), said derivative being a reaction mixture prepared inthe same manner as in Example 11 and being formed of formaldehyde andthe diguanamine bonded together at a molar ratio of 7.3:1, wasdehydrated, followed by the addition of 50 ml of methanol. After beingadjusted to pH 2.0 with a 20% nitric acid, the resulting mixture washeated at 40°-45° C. for 2 hours. The reaction mixture was adjusted topH 8.0 with a 10% aqueous solution of sodium hydroxide. From thesolution, methanol and water were removed under reduced pressure and asolid was then filtered off, whereby a viscous liquid was obtained. As aresult of an analysis of the liquid, it was found that 4.9 equivalentsof N-methoxymethyl groups were bonded to one mole of the diguanamine(2).

As is understood from Examples 15 and 16, the N-methylol derivative ofeach diguanamine, said derivative pertaining to the present invention,readily undergoes an alkyl-etherification reaction with an alcohol undermild conditions, thus having excellent reactivity and can provideN-alkoxymethylated derivatives of the N-methylol derivative, saidalkoxymethylated derivatives being extremely useful as resinintermediates.

EXAMPLE 17 Preparation of a Primary Condensate of N-methylol Diguanamine(2)

To 15.1 g (0.05 mole) of the diguanamine (2) obtained in the same manneras in Example 4, 13.1 g of paraformaldehyde (80% grade) (0.35 mole interms of 100% formaldehyde) and 50 ml of methanol were added. Theresulting solution was adjusted to pH 13.2 with a 20% aqueous solutionof potassium hydroxide under stirring, followed by heating at 80° C. forone hour under stirring. After the completion of the heating, thereaction mixture was adjusted to pH 8.0 with a 10% aqueous solution ofhydrochloric acid. The resulting precipitate was filtered off, whereby aclear solution was obtained. As a result of an analysis of the resinousproduct obtained by the solvent removal of the clear solution, it wasfound to be a primary condensate of N-methylol diguanamine, saidcondensate being formed of the diguanamine (2) and formaldehydemethylol-bonded at a ratio of 6.0 moles of the latter to one structuralunit of the former and having an average addition condensation degree of1.3.

EXAMPLE 18 Preparation of a Primary Condensate of a Diguanamine (1)

To 15.7 g (0.05 mole) of the diguanamine (1) obtained in the same manneras in Example 1, 18.8 g of paraformaldehyde (80% grade) (0.5 mole interms of 100% formaldehyde) and 50 ml of n-butanol were added. Understirring, the solution was adjusted to pH 11.0 with a 10% aqueoussolution of sodium hydroxide. The reaction mixture was heated at 60° C.for 30 minutes under stirring, followed by the adjustment to pH 3.0 witha 20% aqueous solution of nitric acid. The reaction mixture was heatedfor 2 hours under reflux temperature conditions and stirring while beingdehydrated. After the completion of the heating, the reaction mixturewas adjusted to pH 8.0 with a 10% aqueous solution of sodium hydroxide.The resulting precipitate was filtered off, whereby a homogeneous andclear solution was obtained. As a result of an analysis of the resinousproduct obtained by the solvent removal of the solution, it was found tobe a primary condensate of an etherified diguanamine formed of thediguanamine (1) and formaldehyde methylol-bonded at a ratio of 1.9 molesof the latter to one structural unit of the former, containing butylether groups and having an average addition condensation degree of 1.6.

EXAMPLE 19 Polymerization of an N-methylol Derivative of a Diguanamineand Ultraviolet Light Resistance Test of the Resin so Obtained

In 10 ml of n-butyl alcohol, 5.0 g of an N-methylol derivative of thediguanamine (1), which had been obtained in the same manner as inExample 10 and was formed of the diguanamine (1) and formaldehyde bondedtogether at a ratio of 7.2 moles of the latter to one mole of theformer, were dissolved, followed by the addition of 0.025 g ofp-toluenesulfonic acid as a curing catalyst. The resorting solution wascoated on a galvanized sheet steel and then, heated and cured at 140° C.for 20 minutes.

Using a germicidal lamp (manufactured by Toshiba Corporation; 19W) as anultraviolet light source, the sheet steel so coated, that is, a testsheet steel, was exposed for 200 hours to ultraviolet light at avertical distance of 25 cm. The surface gloss of the test sheet steelwas measured in accordance with JIS K 5400 (specular reflection at 60°).As a result, the gloss retention was found to be 97%.

EXAMPLE 20 Polymerization of an N-methylol Derivative of a Diguanamineand Ultraviolet Light Resistance Test of the Resin so Obtained

In 10 ml of n-butyl alcohol, 5.0 g of an N-methylol derivative of thediguanamine (2), which had been obtained in the same manner as inExample 11 and was formed of the diguanamine (2) and formaldehyde bondedtogether at a molar ratio of 7.3:1, were dissolved, followed by theaddition of 0.025 g of p-toluenesulfonic acid as a curing catalyst. Theresulting solution was coated on a galvanized sheet steel and then,heated and cured at 140° C. for 20 minutes.

Using a germicidal lamp (manufactured by Toshiba Corporation; 19W) as anultraviolet light source, the sheet steel so coated, that is, a testsheet steel, was exposed for 200 hours to ultraviolet light at avertical distance of 25 cm. The surface gloss of the test sheet steelwas measured in accordance with JIS K 5400 (specular reflection at 60°).As a result, the gloss retention was found to be 98%.

As has been shown in Examples 19 and 20, the N-methylol derivatives ofdiguanamines, said derivatives relating to the present invention, hadexcellent properties including superb polymerizability and ah extremelysmall deterioration in gloss under ultraviolet rays.

EXAMPLE 21 Crease Resistance Test of a Fiber Treatment Containing anN-methylol Derivative of a Diguanamine

Deionized water was added to an N-methylol derivative of the diguanamine(1), which had been prepared in the same manner as in Example 10 and wasformed of the diguanamine (1) and formaldehyde bonded together at amolar ratio of 7.2:1, to prepare its 10 wt. % aqueous solution. To thesolution, 3 wt. % (relative to the solid content of the derivative) ofammonium secondary phosphate were added as a catalyst. A cotton cloth(cotton broadcloth No. 60) was dipped in the resulting solution,followed by padding. The cloth was subjected to preliminary drying at80° C. for 5 minutes and then, heated at 140° C. for 5 minutes.

A crease resistance test was conducted in accordance with JIS L 1059(Monsanto method), using the cloth so treated. As a result, it was foundthat the cloth had a crease resistance of 86%, thus exhibiting excellentcrease resistance.

Each N-methylol derivative of a diguanamine, said derivative pertainingto the present invention, can impart, as demonstrated above, excellentcrease resistance and the like to fibers when they are treated with thederivative. A thermosetting composition containing the diguanaminederivative therein is therefore extremely useful as a fiber treatment.

EXAMPLE 22 Curing Test of a Water-base Paint Resin Containing anN-methylol Derivative of a Diguanamine

To a solution obtained by gradually adding 1.84 g ofdimethylethanolamine to 40.0 g of "Almatex WA 911" (product of MitsuiToatsu Chemicals, Inc., NV: 60%) under stirring and then adjusting itsnonvolatile content to 20% with deionized water, a 50 wt. % aqueoussolution of 6.0 g of an N-methylol derivative of the diguanamine (1),which had been prepared in the same manner as in Example 10 and wasformed of formaldehyde and the diguanamine (1) bonded together at amolar ratio of 7.2:1, was added and mixed. The resulting resin solutionso obtained was coated on a galvanized sheet steel and then, heated at160° C. for 20 minutes.

On the coating film of the steel sheet so coated, cissing, blisters,discoloration or the like was not observed at all. The surface gloss ofthe coating film was measured in accordance with JIS K 5400 (specularreflection at 60°). As a result, the film was found to have a surfacegloss of 98%, thus exhibiting outstanding smoothness and gloss.Furthermore, no peeling was observed on the film even after rubbing thefilm surface 50 times with an acetone-soaked cloth. It was, therefore, afully cured and excellent coating film.

EXAMPLE 23 Curing Test of a Water-base Paint Resin Containing anN-methylol Derivative of a Diguanamine

To a solution obtained by gradually adding 1.84 g ofdimethylethanolamine to 40.0 g of "Almatex WA 911" (product of MitsuiToatsu Chemicals, Inc., NV: 60%) under stirring and then adjusting itsnonvolatile content to a 20% with deionized water, a 50 wt. % aqueoussolution of 5.9 g of an N-methylol derivative of the diguanamine (2),which had been prepared in the same manner as in Example 11 and wasformed of formaldehyde and the diguanamine (2) bonded together at amolar ratio of 7.3:1, was added and mixed. The resulting resin solutionso obtained was coated on a galvanized sheet steel and then, heated at160° C. for 20 minutes.

On the coating film of the steel sheet, cissing, blisters, discolorationor the like was not observed at all. The surface gloss of the coatingfilm was measured in accordance with JIS K 5400 (specular reflection at60°). As a result, the film was found to have a surface gloss of 94%,thus exhibiting outstanding smoothness and gloss. Furthermore, nopeeling was observed on the film even after rubbing the film surface 50times with an acetone-soaked cloth. It was, therefore, a fully cured andexcellent coating film.

As has been demonstrated in Examples 21-23, each diguanamine derivativeaccording to the present invention has excellent water reducibility anda thermosetting composition containing the derivative therein is notonly excellent as a resin to be used in an aqueous system, such as awater-base paint resin, adhesive resin or fiber treatment but alsoexhibits excellent curing and crosslinking properties when used as apaint resin. It is therefore extremely useful for a wide variety ofapplications.

EXAMPLE 24 Curing Test of a Water-base Paint Resin Containing anN-methoxymethyl Derivative of a Diguanamine

To a solution obtained by gradually adding 1.84 g ofdimethylethanolamine to 40.0 g of "Almatex WA 911" (product of MitsuiToatsu Chemicals, Inc., NV: 60%) under stirring and then adjusting itsnonvolatile content to 20% with deionized water, a 50 wt. % solution of6.8 g of an N-methoxymethyl derivative of the diguanamine (1), which hadbeen prepared in the same manner as in Example 15 and was formed offormaldehyde and the diguanamine (1) bonded together at a molar ratio of5.3:1, in a 50:50 (by weight) mixed solvent of butyl cellosolve andwater as well as 0.15 g of p-toluenesulfonic acid were added and mixed.The resulting resin solution so obtained was coated on a galvanizedsheet steel and then, heated at 160° C. for 20 minutes.

On the coating film of the steel sheet, cissing, blisters, discolorationor the like was not observed at all. The surface gloss of the film wasmeasured in accordance with JIS K 5400 (specular reflection at 60°). Asa result, the film was found to have a surface gloss of 96%, thusexhibiting outstanding smoothness and gloss. Furthermore, no peeling wasobserved on the film even after rubbing the film surface 50 times withan acetone-soaked cloth. It was, therefore, a fully cured and excellentcoating film.

As has been demonstrated above, each etherified diguanamine according tothe present invention has excellent polymerizability and in addition, athermosetting resin composition which contains the etherifieddiguanamine and a resin reactive therewith and therefore curable isextremely useful as a water-base paint resin.

EXAMPLE 25 Polymerization of an N-methoxymethylated Diguanamine and aWeathering Test of the Resin so Obtained

In 10 g of methyl isobutyl ketone, 4.9 g of an N-methoxymethylderivative of the diguanamine (2), which had been obtained in the samemanner as in Example 16 and was formed of formaldehyde and thediguanamine (2) bonded together at a molar ratio of 4.9:1, weredissolved. To the resulting solution, 47.2 g of "Almatex P 646" (productof Mitsui Toatsu Chemicals, Inc., NV: 60%) were added and mixed. Theresulting resin solution was coated on a galvanized sheet steel andthen, cured by heating it at 180° C. for 50 minutes.

An exposure test of the sheet steel thus coated was conducted for 500hours using a weather-o-meter. Neither blisters nor discoloration wasobserved on the surface of the coating film of the sheet steel. Thesurface gloss of the coating film was measured in accordance with JIS K5400 (specular reflection at 60°). As a result, the gloss retention wasfound to be 95%.

EXAMPLE 26 Polymerization of a Primary Condensate of EtherifiedDiguanamine and a Weathering Test of the Condensate so Obtained

In 10 g of methyl isobutyl ketone, 5.0 g of a primary condensate of theetherified diguanamine (1), which had been obtained in the same manneras in Example 18 and had an average addition condensation degree of 1.6per structural unit of the diguanamine (1) were dissolved. To theresulting solution, 47.2 g of "Almatex P 646" (product of Mitsui ToatsuChemicals, Inc., NV: 60%) were added and mixed. The resulting resinsolution was coated on a galvanized sheet steel and then, cured byheating it at 160° C. for 30 minutes.

An exposure test of the sheet steel thus coated was conducted for 500hours using a weather-o-meter. Neither blisters nor discoloration wasobserved on the surface of the coating film of the sheet steel. Thesurface gloss of the coating film was measured in accordance with JIS K5400 (specular reflection at 60°). As a result, the gloss retention wasfound to be 97%.

As has been demonstrated in Examples 25 and 26, each of etherifieddiguanamines and these primary condensates according to the presentinvention have excellent polymerizability. In addition, a cured productobtained from a thermosetting resin composition containing therein theetherified derivative or the primary condensate and a resin curablethrough a reaction therewith has excellent weather resistance. It is,therefore, extremely useful as a paint resin.

EXAMPLE 27 Curing Test of an Epoxy-containing Resin with a Diguanamine(1)

Dissolved in 100.0 g of butyl cellosolve were 100 g of anepoxy-containing resin ("Epicoat #828"; product of Shell Kagaku K. K.).To the resulting solution, 19.6 g of the diguanamine (1) prepared in thesame manner as in Example 1 were added and dissolved, whereby a resinsolution was prepared. The resin solution was coated on a galvanizedsheet steel, followed by heating at 110° C. for 30 minutes and then,200° C. for 40 minutes. No peeling was observed on the coating film ofthe sheet steel so heated even after rubbing the film surface 50 timeswith a toluene-soaked cloth. It was a fully cured, transparent,excellent coating film.

EXAMPLE 28 Curing Test of an Epoxy-containing Resin with a Diguanamine(2)

In a similar manner to Example 27 except that 18.9 g of the diguanamine(2) prepared in the same manner as in Example 3 were used instead of19.6 g of the diguanamine (1) prepared in the same manner as in Example1, a resin solution was prepared and a coating film curing test of thefilm was conducted.

No peeling was observed on the coating film of the sheet steel so heatedeven after rubbing the film surface 50 times with a toluene-soakedcloth. It was a fully cured, transparent, excellent coating film.

EXAMPLE 29 Storage Stability Test of a Thermosetting Resin Composition

In each example, an epoxy-containing resin and the diguanamine shown inTable 3 were blended in the amounts indicated in the same table. Theresulting blend was kneaded in a twin roll, which had been heated to90°-110° C. in advance, for 15-30 minutes until the blend became fullyuniform. The blend was taken out in the form of a sheet and then ground.The resulting sample was left over in a drier maintained at 40° C.,whereby its storage stability was judged. The results are shown in Table3.

As can be seen from Table 3, each thermosetting resin compositionaccording to the present invention has been found to have excellentstorage stability.

                                      TABLE 3                                     __________________________________________________________________________    Epoxy-containing resin                                                                              Diguanamine    Storage                                               Amount blended Amount blended                                                                         stability                                Kind         (parts by weight)                                                                      kind  (parts by weight)                                                                      at 40° C.                         __________________________________________________________________________    Example                                                                            Epicoat #828                                                                          100.0    Diguana-                                                                            19.6     At least                                 29-1 (Shell           mine (1) in    3 months                                      Kagaku K.K.)     Example 1                                               Example                                                                            Epicoat #828                                                                          100.0    Diguana-                                                                            18.9     At least                                 29-2 (Shell           mine (2) in    3 months                                      Kagaku K.K.)     Example 4                                               __________________________________________________________________________

EXAMPLE 30 Flexibility Test of a Cured Resin Product Obtained From aThermosetting Resin Composition

Blended were 100 g of an epoxy-containing resin ("Epicoat #828; productof Shell Kagaku K. K.) and 19.6 g of the diguanamine prepared in thesame manner as in Example 1. They were kneaded in a twin roll, which hadbeen heated at 90°-110° C. in advance, for 30 minutes until the blendbecame fully uniform. The blend was then taken out in the form of asheet and then ground. The resulting sample was cured at 190° C. for 3hours to obtain a cured resin product. The Charpy impact resistance ofthe cured resin product was measured as an index for flexibility. Theresults are shown in Table 4.

Incidentally, another cured resin product was produced as a comparativeexample under optimal curing conditions in a similar manner to the aboveexcept the dicyandiamide was used instead of the diguanamine in itsoptimum blending amount, and its Charpy impact resistance was measured.

                  TABLE 4                                                         ______________________________________                                        Amount of      Amount of            Charpy                                    EP #828, an    a diguana-           impact                                    epoxy-         mine or     Curing   strength                                  containing     dicyandiamide                                                                             Condi-   (kg · cm/                        resin, blended blended     tions    cm.sup.2)                                 ______________________________________                                        Example 30                                                                            100.0 g    19.6 g      190° C./                                                                      8.0                                                                    3 hr                                           Compar- 100.0 g     5.5 g      170° C./                                                                      3.0                                     ative                          1 hr                                           Example 3                                                                     ______________________________________                                    

As is shown in Table 4, a cured resin product available from eachthermosetting resin composition according to the present invention hasbeen found to have excellent flexibility.

EXAMPLE 31 Weathering Test of a Cured Coating Film Obtained from aThermosetting Resin Composition

Dissolved in 200 g of butyl cellosolve were 100.0 g of anepoxy-containing resin ("Almatex PD #7610"; product of Mitsui ToatsuChemicals, Inc.; epoxy equivalent of solid: 530). The diguanamine (11.1g) prepared in the same manner as in Example 1, was add to and dissolvedin the resulting solution, whereby a resin solution was prepared. Theresin solution was coated on a galvanized sheet steel and then heatedand cured at 200° C. for 40 minutes.

A weathering test was conducted by exposing the sheet steel so coated tolight for 300 hours under a weather-o-meter. The surface gloss of thecoating film on the sheet steel was measured in accordance with JISK-5400 (specular reflection at 60°). As a result, the gloss retentionwas found to be 94%.

As has been demonstrated above, a cured resin product obtained from eachthermosetting resin composition according to the present invention hasbeen found to have excellent weatherability and is extremely useful as apaint resin.

EXAMPLE 32 Test on a Coating Film of a Powder Coating Resin Obtainedfrom a Thermosetting Resin Composition

A resin solution of the thermosetting resin composition prepared in thesame manner as in Example 31 was heated under reduced pressure to removea solvent therefrom, whereby a resin was obtained in a solid form. Thesolid resin was coarsely ground in a coarse grinder, followed by finegrinding in an atomizer. The finely-ground particles so obtained weresifted through a 150-mesh sieve. Those passed through the sieve wereemployed for a test as a powder coating resin. The powder coating resinwas coated on a bonderized sheet steel by electrostatic coating to givea film thickness of about 50 μm, and then heated at 200° C. for 40minutes.

The coating film of the sheet steel so coated and heated was found tohave good smoothness according to visual judgment. Furthermore, nopeeling was observed on the film even after rubbing the film surface 50times with a toluene-soaked cloth. It was a fully cured, excellentcoating film.

Using a germicidal lamp (manufactured by Toshiba Corporation; 19W) as anultraviolet light source, the sheet steel so coated, that is, a testsheet steel was exposed for 200 hours to ultraviolet light at a verticaldistance of 25 cm. Neither blisters nor discoloration was observed onthe surface of the coating film of the sheet steel. The surface gloss ofthe test sheet steel was measured in accordance with JIS K 5400(specular reflection at 60°). As a result, the gloss retention was foundto be 96%. The coating film thus had excellent ultraviolet lightresistance.

EXAMPLE 33 Adhesion Test of a Thermosetting Resin Composition

Blended were 100 g of an epoxy-containing resin ("Epicoat #828"; productof Shell Kagaku K. K.) and 15.7 g of the diguanamine (1) prepared in thesame manner as in Example 1. They were kneaded in a twin roll, which hadbeen heated to 90°-110° C. in advance, until they were fully andhomogeneously mixed. Using the resin so kneaded, steel sheets wereadhered. The resin was then cured at 200° C. for one hour. The resin socured was found to have a tensile shear adhesive strength of 176 kg/cm²at 25° C.

As has been demonstrated above, each thermosetting resin compositionaccording to the present invention has been found to have excellentadhesion and is extremely useful as an adhesive resin or the like.

EXAMPLE 34

A polypropylene resin composition, which consisted of 84 parts by weightof "Mitsui NOBLEN BJH" (trade name for polypropylene resin manufacturedby Mitsui-Toatsu Chemicals Inc.), 15 parts by weight of the diguanamine[formula (1)] obtained in Example 1 and 1 part by weight of dilaurylthiodipropionate, was kneaded at 190° C. for 6 minutes through a mixingroll and then kneaded and pelletized by an extruder. The resultingpellets were molded by an injection molding machine so that test piecesof 1/16 inch in thickness were prepared for the determination offlammability.

Using those test pieces, a test was conducted following the verticalflammability testing method specified under Subject 94 of UnderwritersLaboratories Inc., U.S.A. Their flammability was found to be Level V-1.No. melt dripped during combustion and each test piece so testedretained its original shape well. The polypropylene resin compositiontherefore had excellent frame retardancy.

EXAMPLE 35

A polypropylene resin composition, which consisted of 75 parts by weightof "Mitsui NOBLEN BJH" (trade name for polypropylene resin manufacturedby Mitsui-Toatsu Chemicals Inc.), 6 parts by weight of the diguanamine[formula (1)] obtained in Example 1, 18 parts by weight of "Exolit 422"(trade name for ammonium polyphosphate manufactured by Hoechst A. G.)and 1 part by weight of dilauryl thiodipropionate, was treated in asimilar manner to Example 34 to prepare its test pieces. Using thosetest pieces, a flammability test was conducted in the same manner as inExample 34. Their flammability was found to be Level V-0 and each testpiece so tested retained its original shape well. In addition, thecombined use of the diguanamine of this invention with the phosphoruseswas found to achieve a greater improvement in flame retardancy owing totheir synergistic effects.

EXAMPLES 36-39

A polyethylene resin composition, which consisted of 75 parts by weightof "HIZEX 5100E" (trade name for polyethylene resin manufactured byMitsui Petrochemical Industries Ltd.), 15 parts by weight of thediguanamine [formula (2)] obtained in Example 4 and 10 parts by weightof phosphoruses shown in Table 5, was kneaded at 160° C. for 6 minutesthrough a mixing roll and then kneaded and pelletized by an extruder. Ina similar manner to Example 34, the resulting pellets were treated toprepare test pieces for the determination of flammability and a test wasconducted. The results of the test are shown in Table 5.

As shown in Table 5, the combined use of the diguanamine of thisinvention with the phosphoruses was found to achieve a greaterimprovement in flame retardancy of the polyethylene resin compositionaccording to the present invention. It therefore had excellent flameretardancy.

                  TABLE 5                                                         ______________________________________                                                         Flame retardancy                                                                    Level accord-                                                                 ing to       Melt                                      Ex. No. Phosphoruses   UL Standard 94                                                                             dripping                                  ______________________________________                                        36      2-Ethylhexyldiphenyl                                                                         V-0          Not                                               phosphate                   observed                                  37      Tris(tridecyl)-                                                                              V-1          Not                                               phosphite                   observed                                  38      Diethyl N,N-bis(2-                                                                           V-1          Not                                               hydroxyethyl)amino-         observed                                          methylphophonate                                                      39      Ethylenebistris(2-                                                                           V-1          Not                                               cyanoethyl)phosphin         observed                                          oxide                                                                 ______________________________________                                    

EXAMPLE 40

Eight parts by weight of the diguanamine [formula (1)] obtained inExample 1 and 12 parts by weight of diphenyl acid phosphate were addedand dissolved in 50 parts by weight of butyl cellosolve under heating.The solvent was then removed from the resulting solution to prepare asolid. After 15 parts by weight of the solid so obtained were added to85 parts by weight of "DAPOLE D-600" (trade name for diallyl phthalateresin manufactured by Fudow Co., Ltd.), they were mixed under heating at60°-80° C. The resulting mixture was allowed to cool down. Three partsby weight of dicumyl peroxide was then added to the reaction mixture andmixed, whereby a diallyl phthalate resin composition was obtained. Theresin composition so obtained was poured into a glass-made casting moldand cured so that test pieces of 1/16 inch in thickness were preparedfor the determination of flammability.

Using those test pieces, a test was conducted in a similar manner toExample 34. As a result, it was found that their flammability was LevelV-0 and each test piece so tested retained its original shape well. Thediallyl phthalate resin composition therefore had excellent flameretardancy.

EXAMPLE 41

A nylon resin composition, which had been obtained by adding 10 parts byweight of the diguanamine [formula (1)] obtained in Example 1 to 90parts by weight of pellets of nylon 66, was mixed in a Henschel mixer.The resulting mixture was then kneaded and pelletized by an extruderwhose cylinder temperature was set at 280° C. The resulting pellets weremolded by an injection molding machine so that test pieces of 1/16 inchin thickness were prepared for the determination of flammability.

Using those test pieces, a test was conducted in a similar manner toExample 34. As a result, it was found that their flammability was LevelV-1, they were excellent in char formability and each test piece sotested retained its original shape well. The nylon resin compositiontherefore had excellent flame retardancy.

EXAMPLE 42

To 90 parts by weight of "DAPOLE D-600" (trade name for diallylphthalate resin manufactured by Fudow Co., Ltd.), 7 parts by weight ofthe diguanamine [formula (2)] obtained in Example 3 and 3 parts byweight of isocyanuric acid were added, followed by mixing under heatingto 60°-80° C. The resulting mixture was allowed to cool down. Threeparts by weight of dicumyl peroxide was then added to the reactionmixture and mixed, whereby a diallyl phthalate resin composition wasobtained. The resin so obtained was poured into a glass-made plate andcured so that test pieces of 1/16 inch in thickness were prepared forthe determination of flammability.

Using those test pieces, a test was conducted in a similar manner toExample 34. As a result, it was found that their flammability was LevelV-0 and each test piece so tested retained its original shape well. Thediallyl phthalate resin composition therefore had excellent flameretardancy.

EXAMPLES 43-46

In a similar manner to Example 41 except that the resin compositionemployed in Example 41 was substituted by those shown in Table 6,respectively, test pieces were prepared for the determination offlammability and tests were conducted. The results are shown in Table 6.

EXAMPLE 47

To 44 parts by weight of "Epicoat #828" (trade name for epoxy resinmanufactured by Shell Japan Ltd.), 11 parts by weight of the diguanamine[formula (2)] obtained in Example 4, 9 parts by weight of isocyanuricacid and 36 parts by weight of methyl hexahydrophthalic anhydride wereadded. They were then mixed through a heating roll, whereby an epoxyresin composition was obtained. The resulting resin composition waspoured into a casting mold and cured so that test pieces of 1/16 inch inthickness were prepared for the determination of flammability.

Using those test pieces, a test was conducted in a similar manner toExample 34. The results are shown in Table 6.

EXAMPLE 48

To 80 parts by weight of "ESTAR CR211" (trade name for unsaturatedpolyester resin manufactured by Mitsui Toatsu Chemicals, Inc.), 9 partsby weight of the diguanamine [formula (1)] obtained in Example 1, 11parts by weight of cyanuric acid, 0.7 part by weight of methyl ethylketone peroxide and 0.3 part by weight of cobalt naphthenate were added.They were then mixed by a mixer, whereby an unsaturated polyester resincomposition was obtained. The resulting resin composition was pouredinto a glass-made casting mold and cured so that test pieces of 1/16inch in thickness were prepared for the determination of flammability.

Using those test pieces, a test was conducted in a similar manner toExample 34. The results are shown in Table 6.

                                      TABLE 6                                     __________________________________________________________________________    Resin Composition                  Flame retardancy                                                  Isocyanuric acids                                                                         Level                                                             or          according                                             Diguanamine cyanuric acids                                                                            to UL                                      Ex.               Amount      Amount                                                                             standards                                                                           Melt                                 No.                                                                              Resin   Kind   added.sup.1)                                                                       Kind   added.sup.1)                                                                       94    dripping                             __________________________________________________________________________    43 Nylon 66                                                                              Diguanamine                                                                           7   Isocyanuric                                                                          3    V-0   Not                                             [formula (1)]                                                                             acid              observed                                        Ex. 1                                                              44 Polycarbonate                                                                         Diguanamine                                                                          12   Isocyanuric                                                                          3    V-0   Not                                             [formula (1)]                                                                             acid              observed                                        Ex. 1                                                              45 Polyethylene                                                                          Diguanamine                                                                           8   Tris(2-hydro-                                                                        7    V-0   Not                                     terephthalate                                                                         [formula (2)]                                                                             xyethyl)          observed                                        of Ex. 3    isocyanurate                                           46 Polystyrene                                                                           Diguanamine                                                                          11   Isocyanuric                                                                          9    V-1   Not                                             [formula (2)]                                                                             acid              observed                                        of Ex. 3                                                           47 Epoxy   Diguanamine                                                                          11   Isocyanuric                                                                          9    V-0   Not                                             [formula (2)]                                                                             acid              observed                                        of Ex. 4                                                           48 Unsaturated                                                                           Diguanamine                                                                           9   Isocyanuric                                                                          11   V-1   Not                                     polyester                                                                             [formula (1)]                                                                             acid              observed                                        of Ex. 1                                                           __________________________________________________________________________     .sup.1) Amount added: parts by weight based on 100 parts by weight of the     resin composition                                                        

As shown in Examples 43-48, it has been found that the method for theflame retardation according to the present invention had an excellentflame retarding ability for the wide range of resin compositionsincluding thermoplastic resin and thermosetting resin. It has also beenfound that the combined use of isocyanuric acids or cyanuric acids withthe diguanamine of the present invention achieved a greater improvementin flame retardancy owing to their synergistic effects.

EXAMPLE 49

A polyphenylene ether resin composition, which consisted of 48 parts byweight of poly(2,6-dimethyl-1,4-phenylene ether), that is, apolyphenylene ether resin, 32 parts by weight of polystyrene, 11 partsby weight of the diguanamine [formula (1)] obtained in Example 1,4 partsby weight of isocyanuric acid and 5 parts by weight of "Exolit 422"(trade name for ammonium polyphosphate manufactured by Hoechst A. G.),was mixed in a Henschel mixer. The resulting mixture was then kneadedand pelletized by an extruder. The pellets so obtained were molded by aninjection molding machine so that test pieces of 1/16 inch in thicknesswere prepared for the determination of flammability.

Using those test pieces, a test was conducted in a similar manner toExample 34. As a result, it was found that their flammability was LevelV-0 and each test piece so tested retained its original shape well. Thepolyphenylene ether resin composition therefore had excellent flameretardancy.

EXAMPLE 50

To 100 parts by weight of polypropylene glycol (average molecularweight: 2,000), 0.4 part by weight of water (total water content in thereaction system) was added, followed by mixing for 60 minutes under heatat 40° C. To the reaction mixture, 2,4-tolylene diisocyanate was addedin an amount to give 1.25 as an NCO/OH equivalent ratio and 1.0 as anNCO/H₂ O equivalent ratio, which caused evolution of heat. After thisheat evolution was over, the resulting mixture was heated to 120° C. ata heating rate of 3° C./min. The reaction mixture was maintained at 120°C. for 75 minutes and was stirred, whereby a reaction was conducted. Thereaction mixture was cooled down to 80° C. and then thoroughly mixedwith 30 parts by weight of 2,4-tolylene diisocyanate. The resultingmixture was cooled down to room temperature to prepare a prepolymer.

In the next place, 85 parts of the prepolymer so obtained, 15 parts byweight of the diguanamine [formula (1)] obtained in Example 1, 0.5 partby weight of "Silicone DC-199" (trade name; product of Dow ChemicalCompany), 1.0 part by weight of N-ethylmorpholine, 0.2 part by weight oftriethylamine and 2.3 parts by weight of water were mixed. Immediatelyafter that, the resulting mixture was injected into a mold and caused toexpand in situ, whereby a polyurethane foam was produced.

Using that polyurethane foam, a flammability test was conducted. As aresult, it was found that the foam had self-extinguishing properties andthe foam so tested retained its original shape well. The urethane resincomposition therefore had excellent flame retardancy.

EXAMPLE 51

A polypropylene resin composition, which consisted of 78 parts by weightof "Mitsui NOBLEN BJH" (trade name for polypropylene resin manufacturedby Mitsui Toatsu Chemicals, Inc.), 5 parts by weight of the diguanamine[formula (1)] obtained in Example 1, 15 parts by weight of "Exolit 422"(trade name for ammonium polyphosphate manufactured by Hoechst A. G.), 1part by weight of pentaethylenehexamine and 1 part by weight of dilaurylthiopropionate, was treated in a similar manner to Example 34 so thattest pieces were prepared. Using those test pieces, a flammability testwas conducted in a similar manner to Example 34. As a result, it wasfound that the resin composition was Level V-0, it had excellent selfextinguishing properties and each test piece so tested retained itsoriginal shape well. It was also found that the combined use of thediguanamine of this invention with the phosphoruses and theamino-containing compounds achieved a greater improvement in flameretardancy owing to their synergistic effects.

EXAMPLE 52

Following the procedures of Example 51 except that an ethylene-propylenecopolymer (containing 45 wt. % of propylene) was used instead of thepolypropylene resin, the resulting resin composition was treated and atest was conducted. As a result, it was found that the resin compositionso obtained was Level V-0, it had excellent self-extinguishingproperties and each test piece so tested retained its original shapewell.

In a method for the flame retardation of a resin according to thepresent invention, the combined use of the phosphoruses and theamino-containing compounds was found to achieve a greater improvement inflame retardancy. The resin composition therefore had excellent flameretardancy.

EXAMPLES 53-60

Polypropylene resin compositions, each of which consisted of 76 parts byweight of "Mitsui NOBLEN BJH" (trade name for polypropylene resinmanufactured by Mitsui Toatsu Chemicals, Inc.), 5.5 parts by weight ofthe diguanamine [formula (2)] obtained in Example 3, 17 parts by weightof "Exolit 422" (trade name for ammonium polyphosphate manufactured byHoechst A. G.), 0.5 wt. % of an amino-containing compound shown in Table7 and 1 part by weight of dilauryl thiopropionate, were treated andtested in a similar manner to Example 34. The results are shown in Table7.

As shown in Table 7, in a method for the flame retardation of a resinaccording to the present invention, the combined use of the phosphorusesand the amino-containing compounds with the diguanamine of the presentinvention achieved a greater improvement in flame retardancy. The resincomposition therefore had excellent flame retardancy.

                  TABLE 7                                                         ______________________________________                                                        Flame retardancy                                                                    Level accord-                                                   Amino-contain-                                                                              ing to       Melt                                       Ex. No. ing compounds UL Standard 94                                                                             dripping                                   ______________________________________                                        53      N,N'-Bis(2-amino-                                                                           V-0          Not                                                ethyl)piperazine           observed                                   54      N-(2-Aminoethyl)-                                                                           V-0          Not                                                morpholine                 observed                                   55      N-(2-Aminoethyl)-                                                                           V-0          Not                                                piperidine                 observed                                   56      Dicyandiamide V-0          Not                                                                           observed                                   57      Guanidine.    V-0          Not                                                phosphate salt             observed                                   58      Ethylenediamine-                                                                            V-0          Not                                                formaldehyde (1/2          observed                                           molar ratio)                                                                  reaction product                                                      59      Piperazine-   V-0          Not                                                formaldehyde (1/2          observed                                           molar ratio)                                                                  reaction product                                                      60      Pentamethylene-                                                                             V-0          Not                                                hexamine                   observed                                   ______________________________________                                    

EXAMPLE 61 Thermal Stability Test of Polyphenylene Ether Resin

Mixed in a henschel mixer was a polyphenylene ether resin compositionobtained by adding 0.1 wt. % of the diguanamine [formula (1)] obtainedin Example 1 to a polyphenylene ether resin, which consisted of 45 partsby weight of a poly(2,6-dimethyl-1,4-phenylene ether) component havingan intrinsic viscosity [η] of 0.52, 50 parts by weight of a polystyrenecomponent and 5 parts by weight of a hydrogenated SBS rubber. The resincomposition was kneaded in a molten state and pelletized in a twin-screwextruder whose cylinder temperature had been set at 300° C. Theresulting pellets were molded by an injection molding machine whosecylinder temperature had been set at 290° C. so that test pieces of 1/8inch in thickness were prepared for the determination of Izod impactstrength. Half of the test pieces were left over for 200 hours in acirculating hot-air constant-temperature chamber at 130° C. for an agingtest. Izod impact strength of the test pieces after the aging test wasmeasured in accordance with ASTM D256. Similar to the above, the Izodimpact strength of another half test pieces was measured without aging.The results of Izod impact strength before and after the aging test areshown in Table 8.

EXAMPLES 62 & 63 Thermal Stability Test of Polyphenylene Ether Resin

In a similar manner to the procedures described in Example 61 exceptthat the diguanamine [formula (1)] was replaced by another diguanamine,the resulting resin composition was treated and a test was conducted.The results are shown in Table 8.

COMPARATIVE EXAMPLE 4

In a similar manner to the procedures described in Example 61 except forthe omission of the diguanamine (1) obtained in Example 1, the resultingresin composition was treated and a test was conducted. The results areshown in Table 8.

                  TABLE 8                                                         ______________________________________                                                        Izod impact strength.sup.1)                                                   (1/8" notched)                                                                (kg-cm/cm)                                                           Diguanamine                                                                              Before aging                                                                             After aging                                      ______________________________________                                        Ex. 61   Diguanamine  12.6       7.2 (57)                                              [formula (1)]                                                                 of Ex. 1                                                             Ex. 62   Diguanamine  12.4       6.8 (55)                                              [formula (2)]                                                                 of Ex. 3                                                             Ex. 63   Diguanamine  12.5       7.0 (56)                                              [formula (2)]                                                                 of Ex. 4                                                             Comp.    None         12.3       5.3 (43)                                     Ex. 4                                                                         ______________________________________                                         .sup.1) Each value in parentheses indicates the Izod impact strength afte     the aging in terms of percent retention based on that before the aging.  

EXAMPLES 64-66 Thermal Stability Test of Polyphenylene Ether Resin

In a similar manner to the procedures described in Example 61 exceptthat additives, which will be described below, were added respectivelyto the polyphenylene ether resin composition, the resulting resincomposition was treated and a test was conducted. The results are shownin Table 9.

                  TABLE 9                                                         ______________________________________                                                            Izod impact strength.sup.1)                               Additive            (1/8" notched)                                                          Amount    (kg-cm/cm)                                            Kind          added.sup.2)                                                                            Before aging                                                                             After aging                                ______________________________________                                        Ex. 64 3)         0.1       12.5     8.6 (69)                                 Ex. 65 Triethylene-                                                                             0.3       12.7     9.5 (75)                                        tetramine                                                              Ex. 66 Tris(nonyl-                                                                              0.3       12.7     7.9 (62)                                        phenyl)                                                                       phosphite                                                              ______________________________________                                         .sup.1) Similar to that in Table 8                                            .sup.2) Wt. % based on the amount of the polyphenylene ether resin            3)Pentaerythrityl tetrakis[3(3,5-di-t-butyl-4-hydroxyphenyl)propionate   

EXAMPLE 67 Thermal Stability Test of Polyacetal Resin

A polyacetal resin composition, which had been obtained by adding 1.0wt. % of the diguanamine [formula (2)] obtained in Example 3 to 100parts by weight of a trioxane-dioxolan copolymer which contained 4 wt. %of a dioxolan structural unit having an intrinsic viscosity of 1.6, waspulverized for 40 minutes under heating at 200° C.

The resin composition so pulverized was charged in an open container.The air container was maintained in a circulating air drier set at 220°C. to measure the weight reduction of the resin composition. As aresult, it was found that the thermal depolymerization rate of the resincomposition was 0.68 wt. %/min. Incidentally, the thermaldepolymerization rate of a diguanamine-free resin composition was 2.9wt. %/min.

EXAMPLE 68 Thermal Stability Test of Polyacetal Resin

In a similar manner to the procedures described in Example 67 exceptthat 1.0 parts by weight of the diguanamine [formula (1)] obtained inExample 1 and 1.0 wt. % of 2,2'-methylenebis(4-methyl-6-t-butylphenol)were added instead of 1.0 wt. % of the diguanamine [formula (2)]obtained following the procedures in Example 3, the resulting resincomposition was treated and a test was conducted. As a result, thedepolymerization rate of the resulting resin composition was found to be0.08 wt. %/min.

As shown in Examples 67 and 68, the polyacetal resin compositionsaccording to the present invention had significantly improved thermalstability.

EXAMPLE 69 Thermal Stability Test of Polyethylene Resin

A polyethylene resin composition, which consisted of 100 parts by weightof "Hizex 5100E" (trade name for polyethylene resin manufactured byMitsui Petrochemical Industries Ltd.), 1.0 part by weight of fine copperparticles and 0.5 part by weight of the diguanamine [formula (1)]obtained in Example 1, was kneaded at 160° C. for 6 minutes through amixing roll and was then compression-molded for 5 minutes at 150° C. and200 Kg/cm², whereby a film sheet was obtained.

Using the film sheet so obtained, an accelerated heat deterioration testwas conducted in an air atmosphere in a circulating hot-air oven set at150° C. The time at which the test piece started discoloration wasrecorded as a deterioration start time. The thermal stability of theresin composition was judged according to the period until thedeterioration start time. The results are shown in Table 10.

In a similar manner to the procedures described above except for theomission of 0.5 part by weight of the diguanamine [formula (1)] obtainedin Example 1, the resulting resin composition was treated and a test wasconducted. The results are shown in Table 10 as "Comparative Example 5".

                  TABLE 10                                                        ______________________________________                                                             Period until initi-                                                           ation of deteriora-                                                Diguanamine                                                                              tion (day)                                               ______________________________________                                        Ex. 69      Diguanamine  20 or more                                                       [Formula (1)] of                                                              Example 1                                                         Comp. Ex. 5 None         1                                                    ______________________________________                                    

EXAMPLE 70 Thermal Stability Test of Polypropylene Resin

A polypropylene resin composition, which consisted of 100 parts byweight of "Mitsui NOBLEN BJH" (trade name for polypropylene resinmanufactured by Mitsui Toatsu Chemicals, Inc.), 1.0 part by weight offine copper particles and 0.3 part by weight of the diguanamine [formula(2)] obtained in Example 3, was kneaded at 190° C. for 6 minutes througha mixing roll and was then compression-molded for 5 minutes at 180° C.and 200 Kg/cm², whereby a film sheet was obtained.

Using the film sheet so obtained, a test was conducted in a similarmanner to the procedures described in Example 69. The results are shownin Table 11.

In a similar manner to the procedures described above except for theomission of 0.3 part by weight of the diguanamine (2) obtained inExample 3, the resulting polypropylene resin composition was treated anda test was conducted. The results are shown in Table 11 as "ComparativeExample 6".

                  TABLE 11                                                        ______________________________________                                                             Period until initi-                                                           ation of deteriora-                                                Diguanamine                                                                              tion (day)                                               ______________________________________                                        Ex. 70      Diguanamine  20 or more                                                       [Formula (2)] of                                                              Example 3                                                         Comp. Ex. 6 None         1                                                    ______________________________________                                    

EXAMPLE 71 Compatibilization Test of Tertiary Resin Composed ofPolyamide Resin, Polyphenylene Ether Resin and Polystyrene Resin

To a resin composition, which consisted of 45 parts by weight of apolyphenylene ether resin component composed ofpoly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity [η]of 0.52, 50 parts by weight of a polystyrene resin component and 5 partsby weight of a hydrogenated SBS rubber component, 8 parts by weight ofthe diguanamine [formula (1)] obtained in Example 1 were added, followedby mixing in a Henschel mixer. The resulting mixture was kneaded in amolten state and pelletized in a twin-screw extruder whose cylindertemperature was set at 300° C. The pellets so obtained (54 parts byweight) were pulverized, to which 50 parts by weight of "Toyobo NylonT-802" (trade name for polyamide resin manufactured by Toyobo Co., Ltd.)were added. The resulting resin composition was mixed in a Henschelmixer and was then kneaded in a molten state and pelletized by atwin-screw extruder whose cylinder temperature was set at 280° C.

As a result of observation of the tertiary resin composition by anelectron microscope, it was found that the resin had a sea-islestructure and spheres having a controlled diameter of about 2.4 μm hadbeen uniformly dispersed in the resin. This method was thereforeexcellent in the compatibilization of a resin.

EXAMPLE 72 Compatibilization Test of Binary Resin Composed ofPolyphenylene Ether Resin and Polyamide-imide Resin

In a Henschel mixer, 70 parts by weight of a polyphenylene ether resincomposed of poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsicviscosity [η] of 0.52, 30 parts by weight of "TORLON 4203" (trade namefor polyamide-imide resin manufactured by Amco Corporation) and 5 partsby weight of the diguanamine [formula (2)] obtained in Example 3 weremixed and then kneaded in a molten state and pelletized in a twin-screwextruder whose cylinder temperature was set at 330° C.

As a result of observation of the binary resin composition so obtainedby an electron microscope, it was found that the molten resin had asea-isle structure and spheres having a controlled diameter of about 3.6μm had been uniformly dispersed in the resin. This process was thereforeexcellent for the compatibilization of a resin.

COMPARATIVE EXAMPLE 7

In a similar manner to the procedures described in Example 72 except forthe omission of the diguanamine (2) obtained in Example 3, a treatmentwas conducted so that a pelletized resin composition was obtained.

As a result of observation of the resin composition by an electronmicroscope, the molten resin had a sea-isle structure in which, however,true spheres and oval spheres of a totally-uncontrolled wide range offrom 0.5 to even 40 μm had been dispersed. Thus, the compatibilizationof those resins was very poor.

EXAMPLE 73 Preparation ofN,N',N",N"'-tetrakis(5-hydroxy-3-oxapentyl)diguanamine

In a 3 l flask equipped with a stirrer, a thermometer, a N₂ inlet tube,a liquid inlet tube and a condenser, 314.4 g (1.0 mole) of thediguanamine [formula (1)] obtained in Example 1 and 1471.9 g (14.0moles) of 5-amino-3-oxapentan-1-ol were charged. After the flask wasfully purged with nitrogen gas, 30.0 g (0.3 mole) of concentratedsulfuric acid were gradually added under stirring. The reaction mixturewas heated gradually under stirring and a reaction was conducted at 210°C. for 20 hours. The resulting reaction mixture was cooled down,followed by neutralization with a 50% aqueous solution of caustic soda.From the reaction mixture, a precipitate was removed by hot filtrationand then, the excess 5-amino-3-oxapentan-1-ol was distilled off underreduced pressure, whereby 674.1 g of a pale-yellow oil were obtained.

As a result of an analysis by liquid chromatography, the crude productso obtained was found to contain 93% of a hydroxyl-containingdiguanamine derivative composed, as a mixture, of2,5-bis[4,6-bis(5-hydroxy-3-oxapentylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptaneand2,6-bis[4,6-bis(5-hydroxy-3-oxapentylamino)-1,3,5-triazin-2-yl]-bicyclo[2,2,1]-heptane.The derivative was thereafter separated and analyzed for identification.In an infrared absorption spectrum, the derivative showed absorptionscorresponding to hydroxyl (wide absorption at 3500 m⁻¹) and triazinering (at 820 cm⁻¹). In a ¹ H nuclear magnetic resonance spectrum, theabsorption (6.5, 6.7 ppm) based on NH₂ group of the starting compounddisappeared and instead, an absorption based on CH₂ group was observedat 3.6 ppm. Its elemental analysis data were found to conform well withthe calculated values as shown below.

    ______________________________________                                        Elemental analysis:                                                                    C          H       N                                                 ______________________________________                                        Found:     52.1%        7.5%    20.8%                                         Calculated:                                                                              52.24%       7.56%   21.01%                                        ______________________________________                                    

EXAMPLE 74 Preparation ofN,N',N",N"'-tetrakis(2-hydroxypropyl)diguanamine

In a 3 l flask equipped with a stirrer, a thermometer, an N₂ inlet tubeand a condenser, 302.3 g (1.0 mole) of the diguanamine [formula (2)]obtained in Example 3, 751.1 g (10.0 moles) of 1-amino-2-propanol, 42.8g (0.8 mole) of ammonium chloride and 274 g of ethylene glycol werecharged. The flask was then fully purged with nitrogen gas. The reactionmixture was heated gradually under stirring and a reaction was conductedfor 20 hours under reflux. The resulting reaction mixture was cooleddown, followed by neutralization with a 50% aqueous solution of causticsoda. From the reaction mixture, a precipitate was removed by hotfiltration and then, the excess 1-amino-2-propanol and ethylene glycolwere distilled off under reduced pressure, whereby 541.4 g of apale-yellow crude product were obtained. As a result of an analysis byliquid chromatography, the crude product so obtained was found tocontain 83% of a hydroxyl-containing diguanamine derivative composed, asa mixture, of 1,3-bis[4,6-bis(2-hydroxypropylamino)-1,3,5-triazin-2-yl]-cyclohexane and1,4-bis[4,6-bis(2-hydroxypropylamino)-1,3,5-triazin-2-yl]-cyclohexane.The derivative was thereafter separated and analyzed for identification.In an infrared absorption spectrum, the derivative showed absorptionscorresponding to hydroxyl and triazine ring. In a ¹ H nuclear magneticresonance spectrum, the absorption based on NH₂ group of the startingcompound disappeared and instead, an absorption based on a CH₂ group wasobserved newly. Its elemental analysis data were found to conform wellwith the calculated values as shown below.

    ______________________________________                                        Elemental analysis:                                                                    C          H       N                                                 ______________________________________                                        Found:     53.7%        7.8%    26.1%                                         Calculated:                                                                              53.91%       7.92%   26.20%                                        ______________________________________                                    

EXAMPLE 75 Preparation of N,N',N",N"'-tetrakis(2-hydroxyethyl)diguanamine

In a 3 l flask equipped with a stirrer, a thermometer, an N₂ inlet tubeand a condenser, 314.4 g (1.0 mole) of the diguanamine [formula (1)]obtained in Example 1, 1221.7 g (20.0 moles) of 2-aminoethanol and 64.2g (1.2 moles) of ammonium chloride were charged. The flaak was thenfully purged with nitrogen gas. The reaction mixture was heatedgradually under stirring and a reaction was conducted for 30 hours underreflux. The resulting reaction mixture was cooled down, followed byneutralization with a 50% aqueous solution of caustic soda. From thereaction mixture, a precipitate was removed by hot filtration and then,the excess 1-aminoethanol was distilled off under reduced pressure,whereby 500.4 g of a pale-yellow crude product were obtained. As aresult of an analysis by liquid chromatography, the crude product soobtained was found to contain 79% of a hydroxyl-containing diguanaminederivative composed of a mixture of2,5-bis[4,6-bis(2-hydroxyethylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]-heptaneand2,6-bis[4,6-bis(2-hydroxyethylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane.The derivative was thereafter separated and analyzed for identification.In an infrared absorption spectrum, the derivative showed absorptionscorresponding to hydroxyl and triazine ring. In a ¹ H nuclear magneticresonance spectrum, the absorption based on NH₂ group of the startingcompound disappeared and instead, an absorption based on a CH₂ group wasobserved newly. Its elemental analysis data were found to conform wellwith the calculated values as shown below.

    ______________________________________                                        Elemental analysis:                                                                    C          H       N                                                 ______________________________________                                        Found:     51.3%        7.0%    28.4%                                         Calculated:                                                                              51.42%       6.99%   28.55%                                        ______________________________________                                    

EXAMPLE 76 Preparation of N,N',N",N"'-tetrakis(4-hydroxyphenyl)diguanamine

In a 3 l flask equipped with a stirrer, a thermometer, an N₂ inlet tubeand a condenser, 302.3 g (1.0 mole) of the diguanamine [formula (2)]obtained in Example 4, 873.0 g (8.0 moles) of p-aminophenol, 32.1 g (0.6mole) of ammonium chloride and 1,400 g of diethylene glycol werecharged. The flask was then fully purged with nitrogen gas. The reactionmixture was heated gradually under stirring and a reaction was conductedfor 30 hours at 200° C. The resulting reaction mixture was cooled down,followed by neutralization with a 50% aqueous solution of caustic soda.A precipitate was removed from the reaction mixture by hot filtration,washed with deionized water and then dried under reduced pressure,whereby 643.9 g of a pale-yellow crude product were obtained. As aresult of an analysis by liquid chromatography, the crude product soobtained was found to contain1,4-bis[4,6-bis(4-hydroxyphenylamino)-1,3,5-triazin-2-yl]-cyclohexane inan amount of 94%. The target product was thereafter separated andanalyzed for identification. As a result, in an infrared absorptionspectrum, the crude product had showed absorptions corresponding tohydroxyl, benzene ring and triazine ring. In a ¹ H nuclear magneticresonance spectrum, the absorption based on NH₂ group of the startingcompound disappeared and instead, an absorption based on a phenyl groupwas observed newly. Its elemental analysis data were found to conformwell with the calculated values as shown below.

    ______________________________________                                        Elemental analysis:                                                                    C          H       N                                                 ______________________________________                                        Found:     64.2%        5.0%    20.8%                                         Calculated:                                                                              64.47%       5.11%   20.88%                                        ______________________________________                                    

EXAMPLE 77 Preparation ofN,N',N",N"'-tetrakis(3-hydroxypropyl)diguanamine

In a similar manner to the procedures described in Example 75 exceptthat 1502.2 g (20.0 moles) of 3-aminopropanol were used instead of1221.7 g (20.0 moles) of 2-aminoethanol, a reaction was conducted andthe resulting reaction mixture was treated, whereby 554.9 g of a crudeproduct were obtained. As a result of an analysis by liquidchromatography, the crude product so obtained was found to contain 84%of a hydroxyl-containing diguanamine derivative composed of a mixture of2,5-bis[4,6-bis(3-hydroxypropylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptaneand2,6-bis[4,6-bis(3-hydroxypropylamino)-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane.The derivative was thereafter separated and in a similar manner toExample 75, analyzed for identification. Its elemental analysis datawere found to conform well with the calculated values as shown below.

    ______________________________________                                        Elemental analysis:                                                                    C          H       N                                                 ______________________________________                                        Found:     54.8%        7.6%    25.4%                                         Calculated:                                                                              54.93%       7.74%   25.62%                                        ______________________________________                                    

EXAMPLE 78 Preparation of N,N',N",N"'-tetraphenyldiguanamine

In a similar manner to Example 75 except that 931.3 g (10.0 moles) ofaniline were used instead of 1221.7 g (20.0 moles) of 2-aminoethanol, areaction was conducted and the resulting reaction mixture was treated,whereby 629.9 g of a crude product were obtained. As a result of ananalysis by liquid chromatography, the crude product so obtained wasfound to contain 89% of a diguanamine derivative composed of a mixtureof 2,5-bis[4,6-dianilino-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane and2,6-bis[4,6-dianilino-1,3,5-triazin-2-yl]-bicyclo[2.2.1]heptane. Thederivative was thereafter separated and in a similar manner to Example75, analyzed for identification. Its elemental analysis data were foundto conform well with the calculated values as shown below.

    ______________________________________                                        Elemental analysis:                                                                    C          H       N                                                 ______________________________________                                        Found:     71.6%        5.5%    22.6%                                         Calculated:                                                                              71.82%       5.54%   22.64%                                        ______________________________________                                    

EXAMPLE 79 Preparation of N-mono(4-methoxycarbonylphenyl)diguanamine

In a similar manner to the procedures described in Example 76 exceptthat 151.2 g (1.0 mole) of methyl p-aminobenzoate were used instead of873.0 g (8.0 moles of p-aminophenol, a reaction was conducted. Thereaction mixture was cooled down, followed by neutralization with a 50%aqueous solution of caustic soda. The precipitate was thereafter removedfrom the reaction mixture by hot filtration, washed with deionized waterand then dried under reduced pressure, whereby a pale yellow crudeproduct was obtained. Subsequent to the extraction from the crudeproduct with ethanol, the solvent was removed from the extract. Theresidue was thereafter dried under reduced pressure, whereby 374.5 g ofan extracted product were obtained. As a result of an analysis by liquidchromatography, the extracted product was found to contain 79% of1-(4,6-diamino-1,3,5-triazin-2-yl)-4-[4-amino-6-(4-methoxycarbonylphenylamino)-1,3,5-triazin-2-yl]-cyclohexane.The target product was separated and analyzed for identification. In aninfrared absorption spectrum, the target product showed absorptionscorresponding to ester and triazine ring. Its elemental analysis datawere found to conform well with the calculated values as shown below.

    ______________________________________                                        Elemental analysis:                                                                    C          H       N                                                 ______________________________________                                        Found:     54.9%        5.5%    32.0%                                         Calculated:                                                                              55.04%       5.54%   32.09%                                        ______________________________________                                    

EXAMPLE 80 Preparation of an Oxaalkyl-containing Diguanamine Derivative

In a 3 l flask equipped with a stirrer, a thermometer, an N₂ inlet tube,a liquid feed tube and a condenser, 157.2 g (0.5 mole) of a diguanamineobtained in Example 1, 15.0 g of potassium hydroxide and 500 g ofN,N-dimethylformamide were charged. The flask was then fully purged withnitrogen gas. The reaction mixture was gradually heated to 130° C., atwhich temperature 1277.8 g (22.0 moles) of propylene oxide weregradually added dropwise to the reaction mixture under stirring. Thedropwise addition was conducted over about 5 hours for the reaction.Even after the completion of the addition of proloylene oxide, thereaction was continued further for about 2 hours at the sametemperature. The reaction mixture was then cooled down, followed byneutralization with a 30% aqueous solution of sulfuric acid. From thereaction mixture, N,N-dimethylformamide was distilled off under reducedpressure and the precipitate was collected by filtration, whereby a paleyellow, highly-viscous product was obtained. As a result of measuring aweight increase of the product, the amount of propylene oxide added inthe reaction was found to be 1062.9 g. As a result of an analysis, theoxaalkyl-containing diguanamine derivative so obtained had an OH valueof 162. Followings are its elemental analysis data found.

    ______________________________________                                        Elemental analysis:                                                                  C            H      N                                                  ______________________________________                                        Found:   60.2%          9.8%   5.6%                                           ______________________________________                                    

EXAMPLE 81 Preparation of an Oxaalkyl-containing Diguanamine Derivative

In a 3 l flask equipped with a stirrer, a thermometer, an N₂ inlet tube,a liquid feed tube and a condenser, 331.5 g ofN,N',N",N"'-tetrakis(2-hydroxypropyl)diguanamine obtained in Example 74and 6.6 g of potassium hydroxide were charged. The flask was then fullypurged with nitrogen gas. The reaction mixture was gradually heated to130° C., at which temperature 2079.3 g of propylene oxide were graduallyadded dropwise to the reaction mixture under stirring. The dropwiseaddition was conducted over about 5 hours for the reaction. Even afterthe completion of the addition of propylene oxide, the reaction wascontinued further for about 2 hours at the same temperature. Thereaction product so obtained was pale yellow and highly-viscous. As aresult of measuring a weight increase of the product, it was found thatthe amount of propylene oxide added after the reaction was 1847.0 g.

As a result of an analysis, the oxaalkyl-containing diguanaminederivative so obtained was found to have an OH value of 93. Followingsare its elemental analysis data found.

    ______________________________________                                        Elemental analysis:                                                                  C            H       N                                                 ______________________________________                                        Found:   60.8%          10.0%   3.9%                                          ______________________________________                                    

EXAMPLE 82 Preparation of an Oxaalkyl-containing Diguanamine Derivative

In a 1 l autoclave equipped with a stirrer, a thermometer, an N₂ inlettube and a liquid feed tube, 134.1 g ofN,N',N",N"'-tetrakis(4-hydroxyphenyl)diguanamine obtained in Example 76,100 g of diethylene glycol dimethyl ether and 2.0 g of potassiumhydroxide were charged. The autoclave was then fully purged withnitrogen gas. The reaction mixture was gradually heated to 120° C., atwhich temperature 440.5 g of ethylene oxide were added to the reactionmixture in portions under stirring. The addition was conducted overabout 5 hours for the reaction. Even after the completion of theaddition of ethylene oxide, the reaction was continued further for about2 hours at the same temperature. After the reaction mixture was cooleddown, the autoclave was fully purged with nitrogen gas. The reactionmixture was then taken out of the autoclave. The reaction mixture soobtained was neutralized with a 30% aqueous solution of sulfuric acid.The diethylene glycol dimethyl ether was distilled off under reducedpressure. The precipitate was then collected by filtration, whereby apale yellow, highly viscous product was obtained. As a result ofmeasuring the weight increase of the product, it was found that theamount of ethylene oxide added in the reaction was 381.5 g.

As a result of an analysis, the oxaalkyl-containing diguanaminederivative so obtained was found to have an OH value of 139. Followingsare its elemental analysis data found.

    ______________________________________                                        Elemental analysis:                                                                  C            H      N                                                  ______________________________________                                        Found:   57.0%          8.1%   5.3%                                           ______________________________________                                    

EXAMPLE 83 Preparation of an Oxaalkyl-containing Diguanamine Derivative

In a 3 l flask equipped with a stirrer, a thermometer, an N₂ inlet tube,a liquid charging tube and a condenser, 208.6 g of an N-methylolderivative of the diguanamine [formula (2)] obtained in Example 3 [with1 mole of the diguanamine of formula (2), 7.3 equivalents of methylolgroup are combined], 200.0 g of diethylene glycol dimethyl ether and 5.0g of potassium hydroxide were charged. The flask was then fully purgedwith nitrogen gas. The reaction mixture was gradually heated to 130° C.,at which temperature 2032.8 g of propylene oxide were gradually addeddropwise to the reaction mixture under stirring. The addition wasconducted over about 8 hours for the reaction. Even after the completionof the addition of propylene oxide, the reaction was continued furtherfor about 2 hours at the same temperature. The reaction mixture was thencooled down, followed by neutralization with a 30% aqueous solution ofsulfuric acid. From the reaction mixture, the diethylene glycol dimethylether was distilled off under reduced pressure. The precipitate was thencollected by filtration, whereby a pale yellow, highly viscous productwas obtained. As a result of measuring the weight increase of theproduct, the amount of propylene oxide added after the reaction wasfound to be 1783.1 g.

As a result of an analysis, the oxaalkyl-containing diguanaminederivative so obtained was found to have an OH value of 86. Followingsare its elemental analysis data found.

    ______________________________________                                        Elemental analysis:                                                                  C            H       N                                                 ______________________________________                                        Found:   60.1%          10.0%   2.7%                                          ______________________________________                                    

EXAMPLE 84 Preparation ofN,N',N",N"'-tetrakis(2-morpholinoethyl)diguanamine

In a similar manner to the procedures described in Example 76 exceptthat 1041.5 g (8.0 moles) of N-aminoethylmorpholine were used instead of873.0 g (8.0 moles) of p-aminophenol, a reaction was conducted and theresulting reaction mixture was treated. As a result of an analysis byliquid chromatography, the crude product so obtained was found tocontain 92% of1,4-bis[4,6-bis(2-morpholinoethylamino)-1,3,5-triazin-2-yl]-cyclohexane.The target product was thereafter separated and analyzed foridentification. In an infrared absorption spectrum, the product showedan absorption corresponding to a triazine ring. Its elemental analysisdata were found to conform well with the calculated values as shownbelow.

    ______________________________________                                        Elemental analysis:                                                                    C          H       N                                                 ______________________________________                                        Found:     57.4%        8.2%    26.1%                                         Calculated:                                                                              57.27%       8.28%   25.97%                                        ______________________________________                                    

EXAMPLE 85

A polypropylene resin composition, which consisted of 84 parts by weightof "Mitsui NOBLEN BJH" (trade name for polypropylene resin manufacturedby Mitsui-Toatsu Chemicals Inc.), 15 parts by weight ofN-mono(4-methoxycarbonylphenyl)diguanamine obtained in Example 79 and 1part by weight of dilauryl thiodipropionate, was kneaded at 190° C. for6 minutes through a mixing roll and then kneaded and pelletized by anextruder. The resulting pellets were molded by an injection moldingmachine so that test pieces of 1/16 inch in thickness were prepared forthe determination of flammability.

Using those test pieces, a flammability test was conducted in a similarmanner to Example 34. As a result, their flammability was found to beLevel V-1. No melt dripped during combustion and each test piece sotested retained its original shape well. The polypropylene resincomposition therefore had excellent flame retardancy.

EXAMPLE 86

A polypropylene resin composition, which consisted of 75 parts by weightof "Mitsui NOBLEN BJH" (trade name for polypropylene resin manufacturedby Mitsui-Toatsu Chemicals Inc.), 6 parts by weight ofN-mono(4-methoxycarbonylphenyl)diguanamine obtained in Example 79, 18parts by weight of "EXOLIT 422" (trade name for ammonium polyphosphatemanufactured by Hoechst A. G.) and 1 part by weight of dilaurylthiodipropionate, was treated in a similar manner to Example 34, wherebytest pieces were prepared.

Using those test pieces, a flammability test was conducted in a similarmanner to Example 34. Their flammability was found to be Level V-0 andeach test piece so tested retained its original shape well. It was alsofound that, in a method for the retardation of a resin according to thepresent invention, the combined use of the diguanamine of the presentinvention with the phosphoruses achieved a greater improvement in flameretardancy. The polypropylene resin composition therefore had excellentframe retardancy.

EXAMPLES 87 & 88

In a similar manner to Example 86 except that diguanamine derivatives asshown in Table 12 were used, respectively, instead ofN-mono(4-methoxycarbonylphenyl)diguanamine obtained in Example 79, testpieces were prepared and a test was conducted. The results are shown inTable 12.

As shown in Table 12, it was found that in a flame-retardation method ofa resin according to the present invention, the diguanamine derivativesof the present invention showed excellent effects on the improvement offlame retardancy and the combined use with the phosphoruses acceleratedthe improvement furthermore.

                  TABLE 12                                                        ______________________________________                                                         Flame retardancy                                                                    Level accord-                                                  Diguanamine    ing to      Melt                                       Ex. No. derivative     UL Standard 94                                                                            dripping                                   ______________________________________                                        87      N,N,N",N"'-tetra-                                                                            V-0         Not                                                kis(2-hydroxyethyl)        observed                                           diguanamine of Ex. 75                                                 88      N,N',N",N"'-tetrakis-                                                                        V-0         Not                                                (2-morpholinoethyl)-       observed                                           diguanamine of Ex. 84                                                 ______________________________________                                    

EXAMPLE 89

A polyethylene resin composition, which consisted of 75 parts by weightof "HIZEX 5100E" (trade name for polyethylene resin manufactured byMitsui Petrochemical Industries, Ltd.), 15 parts by weight ofN,N',N",N"'-tetrakis(2-hydroxypropyl)diguanamine obtained in Example 74and 10 parts by weight of 2-ethylhexyldiphenylphosphate, was kneaded at160° C. for 6 minutes through a mixing roll and then kneaded andpelletized by an extruder. In a similar manner to Example 34, testpieces were prepared from these pellets for the determination offlammability

Using those test pieces, a flammability test was conducted in a similarmanner to Example 34. As a result, their flammability was found to beLevel V-0. No melt dripped during combustion and each test piece sotested retained its original shape well. The method for the flameretardation of a resin according to the present invention had excellenteffects on the improvement of flame retardancy.

EXAMPLE 90

A resin composition, which consisted of 75 parts by weight of anethylene-propylene copolymer (containing 45 wt. % of propylene), 14parts by weight ofN,N',N",N"'-tetrakis(5-hydroxy-3-oxapentyl)diguanamine obtained inExample 73, 10 parts by weight of "EXOLIT 422" (trade name for ammoniumpolyphosphate manufactured by Hoechst A. G.) and 1 part by weight ofdilauryl thiodipropionate, was treated in a similar manner to Example 34to prepare its test pieces.

Using those test pieces, a flammability test was conducted in a similarmanner to Example 34. Their flammability was found to be Level V-0 andeach test piece so tested retained its original shape well.

EXAMPLE 91

A nylon resin composition, which had been obtained by adding 10 parts byweight of N,N',N",N"'-tetrakis(2-hydroxypropyl)diguanamine obtained inExample 74 to 90 parts by weight of pellets of nylon 66, was mixed in aHenschel mixer. The resulting mixture was then kneaded and pelletized byan extruder whose cylinder temperature was set at 280° C. The resultingpellets were molded by an injection molding machine so that test piecesof 1/16 inch in thickness were prepared for the determination offlammability.

Using those test pieces, a test was conducted in a similar manner toExample 34. It was found that their flammability was Level V-1 and theywere excellent in char formability and each test piece so testedretained its original shape well.

EXAMPLE 92

A nylon resin composition, which consisted of 90 parts by weight ofpellets of nylon 66, 7 parts by weight ofN,N',N",N"'-tetrakis(2-hydroxypropyl)diguanamine obtained in Example 74and 3 parts by weight of isocyanuric acid, was treated in a similarmanner to Example 91, whereby test pieces were prepared.

Using those test pieces, a flammability test was conducted in a similarmanner to Example 34. It was found that their flammability was Level V-0and each test piece so tested retained its original shape well. Theresin so obtained therefore showed excellent flame retardancy. It wasalso found that, in a method for the retardation of a resin according tothe present invention, the combined use of isocyanuric acid with thediguanamine derivative of the present invention achieved a greaterimprovement in flame retardancy owing to their synergistic effects.

EXAMPLE 93

In a similar manner to Example 42 except thatN,N',N",N"'-tetrakis(3-hydroxypropyl)diguanamine obtained in Example 77was used instead of the diguanamine [formula (2)] obtained in Example 3,test pieces were prepared for the determination of flammability.

Using those test pieces, a flammability test was conducted in a similarmanner to Example 34. It was found that their flammability was Level V-0and each test piece so tested retained its original shape well. Theresin so obtained therefore showed excellent flame retardancy.

EXAMPLE 94

To 44 parts by weight of "EPIKOTE #828" (trade name for epoxy resinmanufactured by Shell Kagaku K. K.), 11 parts by weight ofN,N',N",N"'-tetrakis(2-hydroxyethyl)diguanamine obtained in Example 75,9 parts by weight of tris(2-hydroxyethyl)isocyanurate and 36 parts byweight of methylhexahydrophthalic anhydride were added and mixed in aheated roll, whereby an epoxy resin composition was obtained. The resincomposition so obtained was poured into a casting mold and cured so thattest pieces of 1/16 inch in thickness were prepared for thedetermination of flammability.

Using those test pieces, a flammability test was conducted in a similarmanner to Example 34. It was found that their flammability was Level V-0and each test piece so tested retained its original shape well. Theepoxy resin composition therefore showed excellent flame retardancy.

EXAMPLE 95

In a similar manner to Example 48 except thatN,N',N",N"'-tetrakis(2-hydroxypropyl)diguanamine obtained in Example 74was used instead of the diguanamine [formula (1)] obtained in Example 1,test pieces were prepared for the determination of flammability.

Using those test pieces, a flammability test was conducted in a similarmanner to Example 34. It was found that their flammability was Level V-1and each test piece so tested retained its original shape well.

EXAMPLES 96-99

In a similar manner to Example 53 except thatN,N',N",N"'-tetrakis(2-hydroxyethyl)diguanamine obtained in Example 75and amino-containing compounds shown in Table 13 were used instead ofthe diguanamine [formula (2)] obtained in Example 3 and amino-containingcompounds as shown in Table 7, respectively, test pieces were prepared.A flammability test was then conducted and results are shown in Table13.

As shown in Table 13, it was found that, in a method for the retardationof a resin according to the present invention, a combined use of thephosphoruses and the amino-containing compound with the diguanaminederivative of the present invention improved the flame retardancy of theresin furthermore. The resin therefore showed excellent flameretardancy.

                  TABLE 13                                                        ______________________________________                                                         Flame retardancy                                                                    Level accord-                                                  Amino-contain- ing to      Melt                                       Ex. No. ing compound   UL Standard 94                                                                            dripping                                   ______________________________________                                        96      N,N'-Bis(3-amino-                                                                            V-0         Not                                                propyl)piperazine          observed                                   97      N-(2-Aminoethyl)-                                                                            V-0         Not                                                morpholine                 observed                                   98      Guanidine.     V-0         Not                                                phosphate salt             observed                                   99      Propylenediamine-                                                                            V-0         Not                                                formaldehyde (1/2          observed                                           molar ratio)                                                                  reaction product                                                      ______________________________________                                    

EXAMPLE 100 Thermal Stability Test of Polyphenylene Ether Resin

In a similar manner to the procedures described in Example 61 exceptthat 0.1 wt. % of N,N',N",N"'-tetrakis(2-hydroxypropyl)diguanamineobtained in Example 74 and 0.3 wt. % of tris(nonylphenyl)phosphite wereused instead of the diguanamine [formula (1)] obtained in Example 1, theresulting resin composition was treated and a test was conducted.

As a result, it was found that Izod impact strength of the resin beforeaging was 12.6, while that after aging was 8.1 and the Izod impactstrength after aging in terms of a percent retention strength was 64%.The resin therefore had excellent thermal stability.

EXAMPLE 101 Thermal Stability Test of Polyacetal Resin

In a similar manner to the procedures described in Example 67 exceptthat N,N',N",N"'-tetrakis(2-hydroxyethyl)diguanamine obtained in Example75 was used instead of the diguanamine [formula (2)] obtained in Example3, a treatment and a test were conducted. As a result, the resincomposition so obtained was found to have a thermal depolymerizationrate of 0.83 wt. %/min.

As described above, a method for the thermal stabilization of a resinaccording to the present invention made it possible to significantlyimprove the thermal stability of the polyacetal resin.

EXAMPLE 102 Thermal Stability Test of Polypropylene Resin

In a similar manner to the procedures described in Example 70 exceptthat N,N',N",N"'-tetrakis(3-hydroxypropyl)diguanamine obtained inExample 77 was used instead of the diguanamine [formula (2)] obtained inExample 3, a film sheet was prepared.

Using the film sheet so obtained, a test was conducted in a similarmanner to Example 69. As a result, it was found that the deteriorationstart time of the film was 20 days and more and the film had remarkablygood thermal stability. The method for the thermal stabilization of aresin according to the present invention was therefore excellent.

EXAMPLE 103 Compatibilization Test of Binary Resin Composed ofPolyphenylene Ether Resin and Polyether Imide Resin

In a Henschel mixer, 60 parts by weight of a polyphenylene ether resincomposed of poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsicviscosity [η] of 0.52, 40 parts by weight of "ULTEM 1000" (trade namefor polyether imide resin manufactured by Engineering Plastics, Ltd.)and 5 parts by weight of N,N',N",N"'-tetraphenyldiguanamine obtained inExample 78 were mixed and then kneaded in a molten state and pelletizedin a twin-screw extruder whose cylinder temperature was set at 300° C.

As a result of observation of the binary resin composition so obtainedby an electron microscope, it was found that the molten resin had asea-isle structure and spheres having a controlled diameter of about 2.8μm had been uniformly dispersed in the resin. This method was thereforeexcellent in the compatibilization of a resin.

EXAMPLE 104 Compatibilization Test of Tertiary Resin Composed ofPolyamide Resin, Polyphenylene Ether Resin and Polystyrene Resin

In a similar manner to the procedures described in Example 71 exceptthat N,N',N",N"'-tetrakis(2-hydroxyethyl)diguanamine obtained in Example75 was used instead of the diguanamine [formula (1)] obtained in Example1, a treatment and a test were conducted.

As a result of observation of the tertiary resin composition so obtainedby an electron microscope, it was found that the resin in a molten statehad a sea-isle structure and spheres having a controlled diameter ofabout 2.8 μm had been uniformly dispersed in the resin. This method wastherefore excellent in the compatibilization of a resin.

EXAMPLE 105

In a 3 l flask equipped with a stirrer, a thermometer and a condenser,300.3 g of paraformaldehyde (80% grade, 8.0 moles in terms of 100%formaldehyde) and 300.3 g of deionized water were charged, followed byadjustment of pH to 8.5 with a 10% aqueous solution of caustic soda. Tothe resultant mixture, 628.7 g (2.0 moles) of the diguanamine [formula(1)] obtained in Example 1 were added and mixed. The resulting mixturewas reacted at 80° C. for 2 hours while its pH was maintained at8.5-9.0. The reaction mixture was adjusted to pH 7.0 with a 20% aqueoussolution of sulfuric acid, whereby an amino resin was obtained.

At the temperature kept at 90° C., 2,300 g of a 1.5 wt. % aqueoussolution of polyvinyl alcohol ("Kuraray POVAL 205", trade name; productof Kuraray Co., Ltd.) were whipped through a dispersion mill and to it,the amino resin obtained above was added under stirring, whereby anemulsion was obtained. The emulsion was cooled down to 40° C., followedby the addition of 8.0 g of dodecylbenzenesulfonic acid. Under low-speedstirring by an anchor agitator, the resultant emulsion was heatedgradually at a heating rate of about 10° C./hour. After the temperaturereached 90° C., the reaction was conducted for two hours at thistemperature, whereby a suspension of polymeric microspheres wasobtained.

After being separated from the suspension by a centrifugal separator,the solid was dried under heat at 150° C. for 4 hours, whereby polymericmicrospheres were obtained in the form of white powder.

It was found that the polymeric microspheres so obtained had excellentsolvent resistance because even when being dipped in a solvent such asisopropanol, methyl ethyl ketone or xylene, they neither swelled norwere dissolved in such a solvent and in addition, they had excellentheat resistance because no fusion was observed even by heating in adrier set at 250° C.

EXAMPLE 106

In a 3 l flask equipped with a stirrer, a thermometer and a condenser,450.4 g of paraformaldehyde (80% grade, 12.0 moles in terms of 100%formaldehyde) and 523.4 g of deionized water were charged, followed byadjustment of pH to 9.0 with a 10% aqueous solution of caustic soda. Tothe resultant mixture, 604.7 g (2.0 moles) of the diguanamine [formula(2)] obtained in Example 4 were added and mixed. The resulting mixturewas reacted at 80° C. for 1 hour while its pH was maintained at 9.0-9.5.The reaction mixture was adjusted to pH 6.0 with a 20% aqueous solutionof sulfuric acid, followed by one-hour reaction at 60° C. The reactionmixture was then adjusted to pH 7.0 with a 10% aqueous solution ofcaustic soda, whereby an amino resin was obtained.

At the temperature kept at 90° C., 3,300 g of a 1.0 wt. % aqueoussolution of polyvinyl alcohol ("Kuraray POVAL 205", trade name; productof Kuraray Co., Ltd.) were whipped through a dispersion mill and to it,the amino resin obtained above was added under stirring, whereby anemulsion was obtained.

In a similar manner to Example 105, a reaction was conducted and theresulting reaction mixture was treated using the emulsion so obtained,whereby polymeric microspheres were obtained in the form of whitepowder.

No melt cohesion was observed even when the polymeric microspheres wereheated in a drier set at 250° C. The polymeric microspheres thereforehad excellent heat resistance.

EXAMPLE 107

In a 3 l flask equipped with a stirrer, a thermometer and a condenser,811.5 g of 37% formalin (10.0 moles in terms of 100% formaldehyde) werecharged, followed by the adjustment of pH to 8.0 with a 10% aqueoussolution of sodium carbonate. To the resultant mixture, 604.7 g (2.0moles) of the diguanamine [formula (2)] obtained in Example 3 were addedand mixed. The resulting mixture was reacted at 90° C. for 2 hours whileits pH was maintained at 8.0-8.5. To the reaction mixture, 40.0 g of oilorange S were added, followed by stirring for one hour, whereby acolored amino resin was obtained.

While the temperature was kept at 90° C., 600 g of a 5.0 wt. % aqueoussolution of polyvinyl alcohol ("Kuraray POVAL 205", trade name; productof Kuraray Co., Ltd.) were whipped through a dispersion mill and to it,the colored amino resin obtained above was added under stirring, wherebyan emulsion was obtained.

In a similar manner to Example 105, a reaction was conducted and thereaction mixture was treated using the emulsion so obtained, wherebypolymeric microspheres were obtained in the form of powder colored invivid orange.

EXAMPLE 108

The polymeric microspheres obtained in accordance with the method ofeach of Example 105-107 were added to "ALMATEX L-1042" (trade name forcold dry type acrylic resin manufactured by Mitsui Toatsu Chemicals,Inc.; NV: 40.0%) to give 30% as PWC and were then kneaded in a paintshaker, whereby a resin solution containing these polymeric microsphereswas obtained. The resulting resin solution was coated on a galvanizedsheet steel, followed by heat treatment at 140° C. for 20 minutes.

Using a fadeometer, the sheet steel so coated was exposed to irradiationfor 50 hours to test the weather resistance of a coated film. As aresult, blisters, discoloration or the like were not observed on thecoated film at all. It therefore showed excellent weather resistance.

As shown in Examples 105-108, it was found that polymeric microspheresexcellent in heat-, solvent- and weather-resistance could be obtainedusing novel specified diguanamines according to the present invention.It was also found that polymeric microspheres which are useful as aresinous colorant excellent in weather resistance, color and the likecould be obtained by coloring the polymeric microspheres with acolorant.

EXAMPLE 109

In a manner similar to Example 34 except that polymeric microspheresobtained following the procedures of Example 106 were used instead ofthe diguanamine [formula (1)] obtained in Example 1, test pieces wereprepared for the determination of flammability.

Using those test pieces, a flammability test was conducted in a similarmanner to Example 34. Their flammability was found to be Level V-1 andeach test piece so tested retained its original shape well. Thepolypropylene resin composition therefore had excellent flameretardancy.

EXAMPLE 110

In a similar manner to Example 35 except that the polymeric microspheresobtained following the procedures of Example 105 were used instead ofthe diguanamine [formula (1)] obtained in Example 1, test pieces for thedetermination of flammability were prepared

Using those test pieces, a flammability test was conducted in a similarmanner to Example 34. Their flammability was found to be Level V-0 andeach test piece so tested retained its original shape well. In a processfor the flame retardation of a resin according to the present invention,the combined use of the polymeric microspheres of the present inventionwith phosphoruses achieved a greater improvement in flame retardancy.This method was therefore excellent.

EXAMPLE 111

A nylon resin composition, which consisted of 90 parts by weight ofpellets of nylon 66, 7 parts by weight of polymeric microspheresobtained following the procedures of Example 105 and 3 parts by weightof isocyanuric acid, was treated in a similar manner to Example 91,whereby test pieces for the determination of flammability were prepared.

Using those test pieces, a flammability test was conducted in a similarmanner to Example 34. It was found that their flammability was Level V-0and each test piece so tested retained its original shape well. Thenylon resin composition therefore showed excellent flame retardancy. Inwas also found that in a method for the flame retardation of a resinaccording to the present invention, the combined use of isocyanuric acidwith polymeric microspheres of the present invention achieved a greaterimprovement in flame retardancy owing to their synergistic effects.

EXAMPLE 112

In a similar manner to Example 94 except that the polymeric microspheresobtained following the procedures of Example 105 were employed insteadof N,N',N",N"'-tetrakis(2-hydroxyethyl)diguanamine obtained in Example75, test pieces for the determination of flammability were prepared.

Using those test pieces, a flammability test was conducted in a similarmanner to Example 34. As a result, their flammability was found to beLevel V-0 and each test piece so tested retained its original shapewell. The polymeric microspheres therefore showed excellent flameretardancy.

EXAMPLE 113

A polypropylene resin composition, which consisted of 76 parts by weightof "Mitsui NOBLEN BJH" (trade name for polypropylene resin manufacturedby Mitsui Toatsu Chemicals, Inc.), 5.5 parts by weight of the polymericmicrospheres obtained following the procedures of Example 105, 17 partsby weight of "Exolit 422" (trade name for ammonium polyphosphatemanufactured by Hoechst A. G.), 0.5 part by weight of pentaethylenehexamine and 1 part by weight of dilauryl thiopropionate, was treated ina similar manner to Example 34 so that test pieces for the determinationof flammability were prepared.

Using those test pieces, a flammability test was conducted in a similarmanner to Example 34. As a result, it was found that the resincomposition was Level V-0, it had excellent self extinguishingproperties and each test piece so tested retained its original shapewell. It was also found that in a method for the flame retardation of aresin according to the present invention, a combined use of phosphorusesand amino-containing compounds with the polymeric microspheres achieveda greater improvement in flame retardancy owing to their synergisticeffects. The resin composition therefore had excellent flame retardancy.

EXAMPLE 114

Preparation of Diguanamine-derivative Containing Polyurethane ResinComposition and Foam Thereof

To 30.0 parts by weight ofN,N',N",N"'-tetrakis(5-hydroxy-3-oxapentyl)diguanamine obtained inExample 73 and 70.0 parts by weight of an oxaalkyl-containingdiguanamine derivative obtained in Example 80, 0.1 part by weight ofwater (total water content in the reaction system) was added, followedby mixing for 60 minutes under heating at 40° C. To the reactionmixture, 2,4-tolylene diisocyanate was added in an amount to give 1.1 asan NCO/OH equivalent ratio and 1.0 as an NCO/H₂ O equivalent ratio,which caused evolution of heat. After this heat evolution was over, theresulting mixture was heated to 120° C. at a heating rate of 3° C./min.The reaction mixture was kept at 120° C. for 75 minutes, followed bystirring for reaction. The reaction mixture was cooled down to 80° C.and then thoroughly mixed with 30 parts by weight of 2,4-tolylenediisocyanate. The resulting mixture was cooled down to room temperatureto prepare a prepolymer.

In the next place, 100 parts of the prepolymer so obtained, 0.5 part byweight of "Silicone DC-199" (product of Dow Chemical Company), 1.2 partsby weight of N-ethylmorpholine, 0.2 part by weight of triethylamine and2.7 parts by weight of water were mixed. Immediately after that, theresulting mixture was injected into a mold and caused to expand in situ,whereby a polyurethane foam was produced.

Using that polyurethane foam, a flammability test was conducted. As aresult, it was found that the foam had self-extinguishing properties andthe foam so tested retained its original shape well. Thediguanamine-derivative-containing polyurethane resin compositiontherefore had excellent flame retardancy.

EXAMPLE 115

In a flask equipped with a stirrer, a thermometer and a condenser, 62.8g (0.2 mole) of the diguanamine [formula (1)] prepared in the samemanner as in Example 1, and 64.9 g of 37% formalin (0.8 mole in terms of100% formaldehyde) were charged. While maintaining the pH of theresulting mixture at 8.0-8.5 with a 10% aqueous solution of pottasiumhydroxide, a reaction was conducted at 90° C. for 60 minutes, whereby anamino resin was obtained. To the resulting amino resin, 2.5 g of pulpdust, 10 g of milled fiber, 0.4 g of diammonium imidesulfonate and 2.0 gof zinc stearate were added, followed by kneading. The mass so obtainedwas dried for 4 hours in a drier set at 80° C., followed bypulverization in a ball mill, whereby a thermosetting moldingcomposition was obtained. Using the composition as a sample, its flowwas measured by circular disc method and its gas releasability uponmolding was also measured so that the flowability upon molding wasjudged. The results are shown in Table 14.

As shown in Table 14, it was found that a thermosetting moldingcomposition according to the present invention had excellent flowabilityupon molding and it was therefore significantly useful for the formingof the moldings complicated in shape.

COMPARATIVE EXAMPLE 8

In a reaction vessel similar to that employed in Example 115, 46.6 g(0.37 mole) of melamine and 92.4 g of 37% formalin (1.14 moles in termsof 100% formaldehyde) were charged. While maintaining the pH of theresulting mixture to 8.0-8.5 with a 10% aqueous solution of potassiumhydroxide, a reaction was conducted at 90° C. for 60 minutes, whereby aresin solution was obtained.

In a similar manner to Example 115, the resulting resin solution wastreated, whereby a molding composition was obtained. The flowability ofthe composition upon molding was judged as in Example 115. The resultsare shown in Table 14.

                  TABLE 14                                                        ______________________________________                                        Properties Tested                                                                            Example 115                                                                              Comp. Ex. 8                                         ______________________________________                                        Flow by circular                                                                             105        87                                                  disc method (mm).sup.1)                                                       Gas releasability                                                                            Good       Usual                                               upon forming                                                                  ______________________________________                                         .sup.1) The test was conducted in accordance with JISK6911.              

EXAMPLE 116

In a flask equipped with a stirrer, a thermometer and a condenser, 30.0g of paraformaldehyde (0.8 mole in terms of 100% formaldehyde) and 50.0g of methanol were charged. The resulting mixture was adjusted to pH8.0-8.5 with triethanolamine, to which 60.4 g (0.2 mole) of thediguanamine [formula (2)] prepared in the same manner as Example 3 wereadded and mixed. While maintaining the pH of the-resulting mixture at8.0-8.5, a reaction was conducted at 70° C. for 2 hours, whereby anamino resin was obtained.

Glass cloths were each impregnated with a liquid formulation of theamino resin to give a solid resin content of 40%. The glass cloths soimpregnated were subjected to desolvation at 80° C. and further to agingat 100° C., whereby prepregs were obtained. Those prepregs were stackedone over the other. The stacked prepregs were held between twomirror-finish stainless plates and cured at 140 ° C. and 30 kg/cm² for15 minutes on a laminating press, whereby a laminate was obtained.

Test results of properties of the laminate are presented in Table 15.

                  TABLE 15                                                        ______________________________________                                        Properties Tested Example 116                                                 ______________________________________                                        Arc-resistance (sec).sup.2)                                                                     210                                                         Insulation resistance                                                                            10.sup.11                                                  (under normal                                                                 condition).sup.2)                                                             Impact strength     5.3                                                       (kg · cm/cm).sup.2)                                                  Bending strength   28                                                         (kg/mm.sup.2).sup.2)                                                          Heat resistance (°C.).sup.2)                                                             190                                                         Light stability.sup.3)                                                                          Good                                                        ______________________________________                                         .sup.2) The test was conducted in accordance with JISK6911.                   .sup.3) A test piece was prepared in accordance with the method employed      for the measurement of water absorption in JISK6911. Using the test piece     a test was conducted for 500 hours in a fadeometer.                      

As shown in Table 15, the formed products obtained from thethermosetting molding composition of the present invention wereexcellent in electrical characteristics, mechanical properties, heatresistance, light stability and the like.

EXAMPLE 117

In a flask equipped with a stirrer, a thermometer and a condenser, 129.7g of 37% formalin (1.6 moles in terms of 100% formaldehyde) werecharged, followed-by the adjustment to pH 9.5 with a 10% aqueoussolution of caustic soda. To the resulting solution, 120.8 g (0.4 mole)of the diguanamine [formula (2)] prepared in the same manner as inExample 4 were added and mixed. While maintaining the pH of theresulting mixture at 9.0-10.0, a reaction was conducted at 60° C. forone hour, whereby an amino resin was obtained. To 148.4 g (solidcontent: 100.0 g) of a liquid formulation of the amino resin, 1.0 g ofammonium nitrate and 2.0 g of calcium stearate were added and mixed. Theresulting mixture and 120.0 g of barium sulfate were gradually added toa kneader and kneaded. To the kneader, 40.0 g of glass-chopped strand(1/2 inch) were added successively. While being uniformly dispersed, theresulting mass was kneaded and then extruded through an extruder intopellets. Those pellets were dried for 4 hours in a drier set at 80° C.,followed by pulverization in a mixer, whereby a thermosetting moldingcomposition was obtained.

Using the molding composition as a sample, molding was conducted by acompression molder so that test pieces of 1/16 inch in thickness wereprepared for the determination of flammability.

Using those test pieces, a test was conducted following the verticalflammability testing method specified under Subject 94 of UnderwritersLaboratories Inc., U.S.A. It was found that their flammability was foundto be Level V-0. It was also found that they had excellentself-extinguishing properties and each test piece so tested retained itsoriginal shape well. The molded products, which had been obtained fromthe thermosetting molding composition described above, therefore hadexcellent flame retardancy.

EXAMPLE 118

In a similar manner to the procedures described in Example 117 exceptthat 120.8 g (0.4 mole) of the diguanamine [formula (2)] prepared in thesame manner as in Example 4 were replaced by 94.3 g (0.3 mole) of thediguanamine [formula (1)] prepared in the same manner as in Example 1and 54.7 g (0.1 mole) of N,N',N",N"'-tetrakis (2-hydroxypropyl)diguanamine obtained following the procedures describedin Example 74, a thermosetting molding composition was obtained and testpieces were prepared for the determination of flammability.

Using those test pieces, a flammability test was conducted in a similarmanner to Example 117. As a result, it was found that their flammabilitywas Level V-0 and each test piece so tested retained its original shapewell. The molded products, which had been obtained from thethermosetting molding composition described above, therefore had anexcellent flame retardancy.

EXAMPLE 119

In a flask equipped with a stirrer, a thermometer and a condenser, 60.0g of paraformaldehyde (1.6 moles in terms of 100% formaldehyde) and130.0 g of methanol were charged, followed by the adjustment to pH 9.5with a 10% aqueous solution of caustic soda. To the resulting mixture,125.6 g (0.4 mole) of the diguanamine [formula (1)] prepared in the samemanner as in Example 1 were added and mixed. While maintaining the pH ofthe resulting mixture at 9.0-10.0, a reaction was conducted at 60° C.for 1 hour, whereby an amino resin was obtained.

To 181.8 g (solid content: 100.0 g) of a liquid formulation of the aminoresin, 1.0 g of zinc nitrate, 5.0 g of zinc stearate and 50.0 g ofcalcium carbonate were added and mixed. A glass mat was thereaftercoated with the resulting mixture on a polyethylene film to give 55% asa solid resin content. After being dried at 80° C. in hot air, theresulting prepreg was covered with another polyethylene film andpressed. As a result, impregnation was accelerated while it wasdefoamed, whereby a sheet-like product was obtained.

The sheet-like product was molded by a compression molder to preparetest pieces for the determination of its properties. Test results of theproperties of the test pieces are shown in Table 16.

                  TABLE 16                                                        ______________________________________                                        Properties Tested Example 119                                                 ______________________________________                                        Bending strength   16                                                         (kg/mm.sup.2)                                                                 Heat resistance (°C.)                                                                    200                                                         Light stability   Good                                                        ______________________________________                                    

As shown in Table 16, the thermosetting molding composition according tothe present invention was found to have excellent mechanical properties,heat resistance, light stability and the like as a sheet moldingmaterial.

EXAMPLE 120

In a 3 l flask equipped with a stirrer, a thermometer and a condenser,375.3 g of paraformaldehyde (80% grade, 10.0 moles in terms of 100%formaldehyde) and 250.0 g of deionized water were charged, followed bythe adjustment of pH to 9.0 with a 20% aqueous solution of caustic soda.To the resultant mixture, 628.7 g (2.0 moles) of the diguanamine[formula (1)] prepared in the same manner as in Example 1 were added andmixed. The resulting mixture was reacted at 80° C. for 2 hours while itspH was maintained at 9.0-9.5. The reaction mixture was then adjusted topH 7.0 with a 20% aqueous solution of sulfuric acid, whereby an aminoresin was obtained.

Deionized water was added to the amino resin to adjust the solid resincontent of the resulting solution to 73.0 wt. %. To the resultingmixture, 3.0 wt. % and 1.5 wt. %, each based on the solid content of theamino resin, of formic acid and sodium dodecylbenzenesulfonate wereadded, respectively and mixed. To the resulting mixture, 30 wt. %, basedon the solid content of the amino resin, of trichlorotrifluoroethanewere added under vigorous stirring. Stirring was continued further forabout four minutes to disperse the resulting mixture uniformly, wherebya thermosetting expansion-forming composition was obtained.

The composition was transferred into a polyethylene-made cylindricalvessel. The vessel with the composition held therein was left over in adrier set at 150° C., subjected to foaming at about 48° C., which wasthe temperature of the composition at the time of foaming, and thencured. The elastic foam so obtained was then heat-treated at 180° C. for40 minutes.

As a result of tests, the elastic foam so obtained was found to have 24g/l bulk density, at least 90% percent shape restoration, 14 mmdeflection at break and 0.14N/mm² tensile strength. It was also foundthat its fire resistance was rated as flame retardant.

EXAMPLE 121

In a 3 l flask equipped with a stirrer, a thermometer and a condenser,300.3 g of paraformaldehyde (80% grade, 8.0 moles in terms of 100%formaldehyde) and 195.4 g of deionized water were charged, followed byadjustment of pH to 10.0 with a 20% aqueous solution of caustic soda. Tothe resultant mixture, 604.7 g (2.0 moles) of the diguanamine [formula(2)] prepared in the same manner as in Example 3 were added and mixed.The resulting mixture was reacted at 70° C. for 1 hour while its pH wasmaintained at 10.0-10.5.

In the next place, 41.6 g (0.4 mole) of sodium bisulfite were added tothe reaction mixture and while maintaining its pH at 10.0-10.5, areaction was conducted at 80° C. for 2 hours. The reaction mixture wasadjusted to pH 7.0 with a 20% aqueous solution of sulfuric acid, wherebya modified amino resin was obtained.

Deionized water was added to the modified amino resin to adjust thesolid resin content of the resulting solution to 74.0 wt. %. To theresulting mixture, 3.0 wt. % and 1.5 wt. %, each based on the solidcontent of the modified amino resin, of formic acid and sodiumalkylsulfonate ("Ratemur PS", trade name; 40% grade, product of KaoCorporation) were added, respectively, and mixed. To the resultingmixture, 20 wt. %, based on the solid content of the modified aminoresin, of pentane were added under vigorous stirring. Stirring wascontinued further for about four minutes to disperse the reactionmixture uniformly, whereby a thermosetting expansion-forming compositionwas obtained.

The composition was treated in a similar manner to Example 120,subjected to foaming at about 37° C., which was the temperature of thecomposition at the time of foaming, and then cured, whereby an elasticfoam was obtained. As a result of tests, the elastic foam so obtainedwas found to have 12 g/l bulk density and 21 mm deflection at break.

EXAMPLE 122

In a 3 l flask equipped with a stirrer, a thermometer and a condenser,300.3 g of paraformaldehyde (80% grade, 8.0 moles in terms of 100%formaldehyde), 170.0 g of deionized water and 100 g of ethanol werecharged, followed by adjustment of pH to 13.0 with a 30% aqueoussolution of caustic soda. To the resultant mixture, 604.7 g (2.0 moles)of the diguanamine [formula (2)] prepared in the same manner as inExample 4 were added and mixed. The resulting mixture was reacted at 80°C. for 3 hours while its pH was maintained at 13.0-13.5. The reactionmixture was then adjusted to pH 7.0 with a 30% aqueous solution ofsulfuric acid, followed by ethanol removal, whereby an amino resin wasobtained.

Deionized water was added to the amino resin to adjust the solid resincontent of the resulting solution to 76.0 wt. %. To the resultingmixture, 1.5 wt. %, 1.5 wt. % and 0.5 wt. %, each based on the solidcontent of the amino resin, of formic acid, sodium alkylsulfonate("Ratemur PS", trade name; 40% grade, product of Kao Corporation) andpolyoxyethylenestearyl ether ("Emulgen 310", trade name; product of KaoCorporation] were added, respectively, and mixed. To the resultingmixture, 20 wt. %, based on the solid content of the amino resin, ofpentane were added under vigorous stirring. Stirring was continuedfurther for about four minutes to disperse the reaction mixtureuniformly, whereby a thermosetting expansion-forming composition wasobtained.

The composition was treated in a similar manner to Example 120,subjected to foaming at about 37° C., which was the temperature of thecomposition at the time of foaming, and was cured, whereby an elasticfoam was obtained. After being heat-treated at 200° C. for 20 minutes,the elastic foam was subjected to milling under about 70% compression.This process was repeated five times.

As a result of tests, the elastic foam so obtained was found to have 15g/l bulk density and at least 90% percent shape restoration. It was alsofound that its fire resistance was rated as flame retardant.

EXAMPLE 123

In a 3 l flask equipped with a stirrer, a thermometer and a condenser,300.3 g of paraformaldehyde (80% grade, 8.0 moles in terms of 100%formaldehyde) land 187.5 g of deionized water were charged, followed byadjustment of pH to 10.0 with a 20% aqueous solution of caustic soda. Tothe resultant mixture, 628.7 g (2.0 moles) of the diguanamine [formula(1)] prepared in the same manner as in Example 1 were added and mixed.The resulting mixture was reacted at 70° C. for 1 hour while its pH wasmaintained at 10.0-10.5. In the next place, 41.6 g (0.4 mole) of sodiumbisulfite were added to the reaction mixture and while maintaining itspH at 10.0-10.5, a reaction was conducted at 80° C. for 2 hours. Thereaction mixture was then adjusted to pH 6.0 with a 10% aqueous solutionof sulfuric acid and a reaction was conducted at 60° C. for one hour,whereby a modified amino resin was obtained.

Deionized water was added to the modified amino resin to adjust thesolid resin content of the resulting solution to 75.0 wt. %. To theresulting mixture, 1.0 wt. %, 1.0 wt. % and 0.5 wt. %, each based on themodified amino resin content, of formic acid, sodium alkylsulfonate("Ratemur PS", trade name; 40% grade, product of Kao Corporation) andsodium polyoxyethyleneoleylethersulfate ("Levenol WX", trade name, 26%grade, product of Kao Corporation) were added, respectively, and mixed.To the resulting mixture, 30 wt. %, based on the solid content of themodified amino resin, of trichlorotrifluoroethane were added undervigorous stirring. Stirring was continued further for about four minutesto disperse the reaction mixture uniformly, whereby a thermosettingexpansion-forming composition was obtained.

The composition was transferred into a polyethylene-made cylindricalvessel. The vessel with the composition held therein was set in atreatment chamber equipped with electroscopes. The composition wasexposed to hypersonic wave having a frequency of 2.45 GHz (powerconsumption of the composition: 110 kw per kg of water) from both thetop and bottom of the chamber to conduct foaming and curing, whereby anelastic foam was obtained. The elastic foam so obtained was then heatedat 200° C. for 20 minutes.

As a result of tests, the resulting elastic foam was found to have 4.2g/l bulk density and at least 90% percent shape restoration.

EXAMPLE 124

To 500.0 g (solid content) of the modified amino resin obtained in thesame manner as described in Example 123, 40.0 g (0.06 mole) ofN,N'N",N"'-tetrakis(5-hydroxy- 3-oxapentyl)diguanamine obtained in thesame manner as described in Example 73 were added and they were mixed,whereby a modified amino resin containing a diguanamine derivative wasobtained.

Deionized water was added to the resin solution to adjust the solidcontent of the resulting solution to be 75.0 wt. %. The resin solutionso obtained showed good water solubility and storage stability.

The resin solution was adjusted and treated in a similar manner toExample 123, whereby a thermosetting expansion-forming composition wasprepared. The thermosetting composition was then cured and treated toprepare an elastic foam.

As a result of tests, the elastic foam was found to have 6.1 g/l bulkdensity and at least 90% percent shape restoration. It was also foundthat its fire resistance was rated as flame retardant.

EXAMPLE 125

In a 3 l flask equipped with a stirrer, a thermometer and a condenser,300.3 g of paraformaldehyde (80% grade, 8.0 moles in terms of 100%formaldehyde) and 240.0 g of deionized water were charged, followed byadjustment of pH to 10.0 with a 20% aqueous solution of caustic soda. Tothe resultant mixture, 147.2 g (0.3 mole) ofN,N',N",N"'-tetrakis(2-hydroxyethyl)diguanamine prepared in the samemanner as in Example 75 and 534.4 g (1.7 moles) of the diguanamine[formula (1)] prepared in the same manner as in Example 1 were added andmixed. The resulting mixture was reacted at 60° C. for 2 hours while itspH was maintained at 10.0-10.5. The reaction mixture was then adjustedto pH 7.0 with a 20% aqueous solution of sulfuric acid, whereby an aminoresin was obtained.

Deionized water was added to the amino resin to adjust the solid resincontent of the resulting solution to be 73.0 wt. %. To the resultingmixture, 3.0 wt. % and 1.5 wt. %, each based on the solid content of theamino resin, of formic acid and sodium alkylsulfonate ("Ratemur PS",trade name; 40% grade, product of Kao Corporation) were added,respectively, and mixed. To the resulting mixture, 20 wt. %, based onthe solid content of the amino resin, of pentane were added undervigorous stirring. Stirring was continued further for about four minutesto disperse the reaction mixture uniformly, whereby a thermosettingexpansion-forming composition was obtained.

The resulting composition was transferred into a polyethylene-madecylindrical vessel. The vessel with the composition held therein wasleft over in a drier set at 150° C., the composition was subjected tofoaming at about 37° C., which was the temperature of the composition atthe time of foaming, and then was cured, whereby an elastic foam wasobtained.

As a result of tests, it was found that the elastic foam had 14 g/l bulkdensity and 24 mm deflection at break and its fire resistance was ratedas flame retardant.

As described in Examples 120-125, it was found that the use of novelspecified diguanamines and derivatives thereof according to the presentinvention made it possible to obtain thermosetting expansion-formingcompositions which could be prepared easily and had excellentdispersibility and solubility in a solvent such as water. It was alsofound that elastic foams having excellent mechanical properties, flameretardancy and the like could be obtained by foaming and curing theabove thermosetting expansion-forming compositions.

We claim:
 1. A thermosetting resin composition comprising anepoxy-containing resin and at least one diguanamine selected fromdiguanamines represented by the following formula (1): ##STR29## whereinthe bonding sites of the 4,6-diamino-1,3,5-triazin-2-yl groups are the2,5- or 2,6-positions, or by the following formula (2): ##STR30##wherein the bonding sites of the 4,6-diamino-1,3,5-triazin-2-yl groupsare the 1,2-, 1,3- or 1,4-positions.
 2. A paint resin compositioncomprising the thermosetting resin composition of claim
 1. 3. A paintresin composition of claim 2, which is a powder coating resincomposition.
 4. An adhesive resin composition comprising thethermosetting resin composition of claim 1.